TWI870556B - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Abstract

The present invention provides a curable resin composition, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, wherein the curable resin composition comprises: at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamide imide precursor; an organic metal complex; and at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3), wherein the content of the compound is 10 to 50,000 ppm relative to the total mass of the composition.

Description

Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

The present invention relates to a curable resin composition, a cured film, a laminate, a method for manufacturing the cured film, and a semiconductor device.

Since resins such as polyimide, polybenzoxazole, and polyamide imide have excellent heat resistance and insulation properties, they are suitable for various applications. The above-mentioned applications are not particularly limited, but for example, for semiconductor devices for packaging, they can be used as materials for insulating films or sealing materials, or as protective films. In addition, they are also used as base films or coverlay films for flexible substrates.

For example, in the above-mentioned applications, resins such as polyimide, polybenzoxazole, and polyamide imide are used in the form of a curable resin composition including at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamide imide precursors. The curable resin composition is applied to a substrate, for example, by coating, to form a photosensitive film, and then exposed, developed, heated, etc. as needed, thereby forming a cured product on the substrate. The above-mentioned polyimide precursor, polybenzoxazole precursor and polyamideimide precursor are cyclized by heating, for example, and become polyimide, polybenzoxazole and polyamideimide in the cured product, respectively. Since the curable resin composition can be applied by a known coating method, it can be said that it has excellent adaptability in manufacturing, for example, the design freedom of the shape, size, and application position of the curable resin composition is high. In addition to the high performance of polyimide, polybenzoxazole, polyamideimide, etc., from the perspective of excellent adaptability in manufacturing, the application expansion of the above-mentioned curable resin composition in the industry is increasingly expected.

For example, Patent Document 1 describes a negative photosensitive resin composition comprising 100 parts by mass of a polyimide precursor of a specific structure, 1 to 20 parts by mass of a photopolymerization initiator, and 0.01 to 10 parts by mass of a monocarboxylic acid compound having 2 to 30 carbon atoms and having one or more functional groups selected from the group consisting of a hydroxyl group, an ether group, and an ester group.

[Patent Document 1] Japanese Patent Application Publication No. 2011-191749

It is required to improve the resolution when forming a pattern composed of a curable resin composition.

The object of the present invention is to provide a curable resin composition having excellent resolution when patterning, a cured film formed by curing the curable resin composition, a cured laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate.

Representative embodiments of the present invention are shown below. ＜1＞ A curable resin composition comprising: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors and polyamide imide precursors; an organic metal complex; and at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2) and a compound represented by the following formula (1-3), wherein the content of the above compounds is 10 to 50,000 ppm relative to the total mass of the composition. [Chemical Formula 1] In formula (1-1), formula (1-2) or formula (1-3), ^R11 and ^R12 each independently represent an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, an aliphatic alkyl group having 1 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure, a quaternary ammonium group and an aliphatic heterocyclic group, or an aliphatic alkyl group having 2 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group and an alkylthio group, ^R21 and ^R22 each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, ^R31 and ^R32 each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. <2> The curable resin composition as described in <1>, wherein the compound is a compound represented by any one of the following formulas (G-1) to (G-12). [Chemical Formula 2] <3> The curable resin composition as described in <1> or <2>, further comprising a photopolymerization initiator. <4> The curable resin composition as described in any one of <1> to <3>, further comprising a crosslinking agent. <5> The curable resin composition as described in any one of <1> to <4>, wherein the organometallic complex is a metallocene compound. <6> The curable resin composition as described in any one of <1> to <5>, wherein the metal contained in the organometallic complex is at least one metal selected from the group consisting of titanium, zirconium and einsteinium. <7> The curable resin composition as described in any one of <1> to <6>, wherein the organometallic complex has photoradical polymerization initiation ability. <8> A curable resin composition as described in any one of <1> to <7>, which is used to form a photosensitive film for negative type development. <9> A curable resin composition as described in any one of <1> to <8>, which is used to form an interlayer insulating film for a redistribution layer. <10> A cured film, which is formed by curing the curable resin composition as described in any one of <1> to <9>. <11> A laminate comprising two or more layers of the cured films as described in <10>, wherein a metal layer is included between any of the cured films. <12> A method for manufacturing a cured film, which comprises: a film forming process, wherein the curable resin composition as described in any one of <1> to <9> is applied to a substrate to form a film. ＜13＞ The method for producing a cured film as described in ＜12＞, which comprises: an exposure process for exposing the above-mentioned film; and a development process for developing the above-mentioned film. ＜14＞ The method for producing a cured film as described in ＜13＞, wherein the exposure light used in the above-mentioned exposure comprises light having a wavelength of 405nm. ＜15＞ The method for producing a cured film as described in ＜13＞ or ＜14＞, wherein the above-mentioned exposure is exposure based on a laser direct imaging method. ＜16＞ The method for producing a cured film as described in any one of ＜12＞ to ＜15＞, which comprises: a heating process for heating the above-mentioned film at 50 to 450°C. ＜17＞ A semiconductor device, which comprises the cured film described in ＜10＞ or the laminated body described in ＜11＞. [Effect of the invention]

According to the present invention, there are provided a curable resin composition having excellent resolution when patterning, a cured film formed by curing the curable resin composition, a laminate including the cured film, a method for manufacturing the cured film, and a semiconductor device including the cured film or the laminate.

The main embodiments of the present invention are described below. However, the present invention is not limited to the specified embodiments. In this specification, the numerical range represented by the symbol "～" refers to the range including the numerical values recorded before and after "～" as the lower limit and upper limit, respectively. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the expected effect of the process can be achieved. In the marking of groups (atomic groups) in this specification, the marking without substitution and unsubstituted includes groups (atomic groups) without substituents, and also includes groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups), but also alkyl groups with substituents (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. In addition, as the light used in exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, electron beams and other actinic rays or radiation can be cited. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate", "(meth)acrylic acid" means both or either "acrylic acid" and "methacrylic acid", and "(meth)acryl" means both or either "acryl" and "methacryl". In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the total solid content refers to the total mass of the components after removing the solvent from all the components of the composition. In addition, in this specification, the solid content concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, unless otherwise specified, the weight average molecular weight (Mw) and number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using, for example, HLC-8220GPC (manufactured by TOSOH CORPORATION) and using as columns guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION). Unless otherwise specified, the molecular weights are determined using THF (tetrahydrofuran) as an eluent. Furthermore, unless otherwise specified, the detection in the GPC measurement is determined using a UV (ultraviolet) ray detector with a wavelength of 254 nm. In this specification, when the positional relationship of each layer constituting a laminate is described as "upper" or "lower", it is sufficient that there are other layers on the upper side or lower side of the layer serving as a reference among the multiple layers concerned. In other words, a third layer or element may be further interposed between the layer serving as a reference and the other layers mentioned above, and the layer serving as a reference and the other layers mentioned above do not need to be in contact. Furthermore, unless otherwise specified, the direction in which the layers are gradually stacked with respect to the substrate is referred to as "upper", or, when there is a photosensitive film, the direction from the substrate toward the photosensitive film is referred to as "upper", and the opposite direction is referred to as "lower". In addition, the setting of the up and down direction is for the convenience of this specification. In actual embodiments, the "up" direction in this specification may also be different from the vertical direction. In this specification, unless otherwise specified, in the composition, each component contained in the composition may include two or more compounds corresponding to the component. In addition, unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component. In this specification, unless otherwise specified, the temperature is 23°C, the air pressure is 101,325Pa (1 atmosphere), and the relative humidity is 50%RH. In this specification, the combination of the better embodiment is the better embodiment.

(Curing resin composition) The curable resin composition of the present invention comprises: at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors and polyamide imide precursors; an organic metal complex; and at least one selected from the group consisting of a compound represented by formula (1-1), a compound represented by formula (1-2) and a compound represented by formula (1-3), wherein the content of the above-mentioned compounds is 10 to 50,000 ppm relative to the total mass of the composition. Hereinafter, at least one resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors and polyamide imide precursors is referred to as a "specific resin", and the compound represented by formula (1-1), the compound represented by formula (1-2) and the compound represented by formula (1-3) are collectively referred to as a "specific compound". [Chemical Formula 3] In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, an aliphatic alkyl group having 1 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure, a quaternary ammonium group and an aliphatic heterocyclic group, or an aliphatic alkyl group having 2 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group and an alkylthio group, R ²¹ and R ²² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, R ³¹ and R ³² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

The curable resin composition of the present invention is preferably used to form a photosensitive film for exposure and development, and is preferably used to form a film for exposure and development using a developer containing an organic solvent. In addition, the curable resin composition of the present invention is preferably used to form a photosensitive film for negative development. In the present invention, negative development refers to development in which the non-exposed part is removed by development during exposure and development, and positive development refers to development in which the exposed part is removed by development. As the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method, for example, the exposure method described in the exposure process in the description of the method for producing a cured film described later, the developer and the development method can be used.

The curable resin composition of the present invention has excellent exposure sensitivity and the chemical resistance of the obtained pattern. The mechanism by which the above effect can be obtained is not clear, but it is speculated as follows.

For example, as described in Patent Document 1, in order to improve chemical resistance, an organic titanium compound or the like is added to a curable resin composition. However, when a composition including an organic metal complex is used for patterning, the organic metal complex aggregates in the film, and there is a case where the resolution is reduced. The curable resin composition of the present invention contains a specific compound in a specific content. It is believed that the organic metal complex contained in the composition is dispersed in a nearly uniform state in the film due to the strong interaction between the specific compound and the organic metal complex. As a result, it is estimated that the resin composition of the present invention has excellent resolution. It is speculated that if the content of the specific compound is 10 ppm or more relative to the total mass of the composition, the dispersibility of the above-mentioned organometallic complex is sufficiently improved, so the resolution is excellent. In addition, it is speculated that if the content of the specific compound is 50,000 ppm or less relative to the total mass of the composition, the influence of the specific compound on the removability of the non-pattern part by the developer is suppressed, and the resolution is excellent.

Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.

<Specific resin> The curable resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors and polyamide imide precursors. The curable resin composition of the present invention preferably contains a polyimide precursor as the specific resin. In addition, the specific resin preferably has a free radical polymerizable group. When the specific resin has a radical polymerizable group, the curable resin composition preferably includes the photoradical polymerization initiator described below as a photosensitive agent, more preferably includes the photoradical polymerization initiator described below as a photosensitive agent and includes the radical crosslinking agent described below, and further preferably includes the photoradical polymerization initiator described below as a photosensitive agent, includes the radical crosslinking agent described below, and includes the sensitizer described below. For example, a negative photosensitive film is formed by such a curable resin composition. In addition, the specific resin may have a polar conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the curable resin composition preferably includes the photoacid generator described below as a photosensitive agent. The curable resin composition can be used to form, for example, a chemically amplified positive photosensitive film or a negative photosensitive film.

[Polyimide precursor] The type of the polyimide precursor used in the present invention is not particularly limited, but it is preferably a polyimide precursor comprising a repeating unit represented by the following formula (2). [Chemical formula 4] In formula (2), ^A1 and ^A2 each independently represent an oxygen atom or NH, ^R111 represents a divalent organic group, ^R115 represents a tetravalent organic group, and ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group.

^A1 and ^A2 in formula (2) each independently represent an oxygen atom or NH, preferably an oxygen atom. ^R111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups. Groups composed of linear or branched aliphatic groups having 2 to 20 carbon atoms, cyclic aliphatic groups having 6 to 20 carbon atoms, aromatic groups having 6 to 20 carbon atoms or combinations thereof are preferred, and groups containing aromatic groups having 6 to 20 carbon atoms are more preferred. As a particularly preferred embodiment of the present invention, a group represented by -Ar-L-Ar- can be exemplified. Wherein, Ar is independently an aromatic group, and L is a group consisting of an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more thereof. The preferred ranges are as described above.

R ¹¹¹ is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one diamine may be used, or two or more diamines may be used. Specifically, a diamine containing a group consisting of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination thereof is preferred, and a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms is more preferred. Examples of aromatic groups include the following.

[Chemical formula 5] In the formula, A is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, -SO ₂ -, -NHCO-, or a combination thereof; more preferably a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -C(=O)-, -S-, or -SO ₂ -; and even more preferably -CH ₂ -, -O-, -S-, -SO ₂ -, -C(CF ₃ ) ₂ -, or -C(CH ₃ ) ₂ -. In the formula, * indicates a bonding site with other structures.

As the diamine, specifically, at least one diamine selected from the group consisting of 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine. ; m- or p-phenylenediamine, diaminotoluene, 4,4’- or 3,3’-diaminobiphenyl, 4,4’-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 4,4’- and 3,3’-diaminodiphenylmethane, 4,4’- and 3,3’-diaminodiphenyl sulfide, 4,4’- and 3,3’-diaminodiphenyl sulfide, 4,4’- or 3,3’-diaminobenzophenone, 3,3’-dimethyl-4,4’-diaminobiphenyl, 2,2’-dimethyl-4,4’-diaminobiphenyl, 3,3’-dimethoxy-4,4’-diaminobiphenyl, 2,2-diaminodiphenyl (4-aminophenyl) propane, 2,2-bis(4-aminophenyl) hexafluoropropane, 2,2-bis(3-hydroxy-4-aminophenyl) propane, 2,2-bis(3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl) propane, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, bis(3-amino-4-hydroxyphenyl) sulfide, bis(4-amino-3-hydroxyphenyl) sulfide, 4,4'-diaminoterphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl] sulfide 、Bis[4-(3-aminophenoxy)phenyl]sulfone、Bis[4-(2-aminophenoxy)phenyl]sulfone、1,4-bis(4-aminophenoxy)benzene、9,10-bis(4-aminophenyl)anthracene、3,3'-dimethyl-4,4'-diaminodiphenylsulfone、1,3-bis(4-aminophenoxy)benzene、1,3-bis(3-aminophenoxy)benzene、1,3-bis(4-aminophenyl)benzene、3,3'-diethyl-4,4'-diaminodiphenylmethane、3,3'-dimethyl-4,4'-diaminodiphenylmethane、4,4'-diaminooctafluorobiphenyl、2 ,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 9,9-bis(4-aminophenyl)-10-hydroanthracene, 3,3',4,4'-tetraaminobiphenyl, 3,3',4,4'-tetraaminodiphenyl ether, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 3,3-dihydroxy-4,4'-diaminobiphenyl, 9,9'-bis(4-aminophenyl)fluorene, 4,4'-dimethyl-3,3'-diaminodiphenylsulfone, 3,3',5,5'-tetramethyl-4,4'-diamino Aminodiphenylmethane, 2,4- and 2,5-diaminoisopropylbenzene, 2,5-dimethyl-p-phenylenediamine, ethylguanidine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, bis(3-aminopropyl)tetramethyldisiloxane, 2,7-diaminofluorene, 2,5-diaminopyridine, 1,2-bis(4-aminophenyl)ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1,5-diaminonaphthalene, diaminotrifluorotoluene, 1,3-bis(4-aminophenyl)hexafluoropropane, 1,4-bis(4-aminophenyl)octafluorobutane, 1 ,5-Bis(4-aminophenyl)decafluoropentane, 1,7-Bis(4-aminophenyl)tetradecafluoroheptane, 2,2-Bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(2-aminophenoxy)phenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-dimethylphenyl]hexafluoropropane, 2,2-Bis[4-(4-aminophenoxy)-3,5-bis(trifluoromethyl)phenyl]hexafluoropropane, p-Bis(4-amino-2-trifluoromethylphenoxy)benzene, 4,4'-Bis(4-amino-2-trifluoromethylphenoxy) )biphenyl, 4,4’-bis(4-amino-3-trifluoromethylphenoxy)biphenyl, 4,4’-bis(4-amino-2-trifluoromethylphenoxy)diphenylsulfone, 4,4’-bis(3-amino-5-trifluoromethylphenoxy)diphenylsulfone, 2,2-bis[4-(4-amino-3-trifluoromethylphenoxy)phenyl]hexafluoropropane, 3,3’,5,5’-tetramethyl-4,4’-diaminobiphenyl, 4,4’-diamino-2,2’-bis(trifluoromethyl)biphenyl, 2,2’,5,5’,6,6’-hexafluorotriphenylmethane and 4,4’-diaminotetraphenyl.

Furthermore, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598 are also preferred.

Furthermore, diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 can also be preferably used.

From the viewpoint of the flexibility of the obtained organic film, R ¹¹¹ is preferably represented by -Ar-L-Ar-. Here, Ar is independently an aromatic group, and L is a group consisting of an aliphatic alkyl group having 1 to 10 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S-, -SO ₂ - or -NHCO-, or a combination of two or more of the foregoing. Ar is preferably a phenylene group, and L is preferably an aliphatic alkyl group having 1 or 2 carbon atoms which may be substituted by a fluorine atom, -O-, -CO-, -S- or -SO ₂ -. The aliphatic alkyl group here is preferably an alkylene group.

Furthermore, from the viewpoint of the i-ray transmittance, R ¹¹¹ is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of the i-ray transmittance and availability, a divalent organic group represented by formula (61) is more preferred. Formula (51) [Chemical Formula 6] In formula (51), R ⁵⁰ to R ⁵⁷ are independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R ⁵⁰ to R ⁵⁷ is a fluorine atom, a methyl group or a trifluoromethyl group. Examples of the monovalent organic group of R ⁵⁰ to R ⁵⁷ include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like. [Chemical Formula 7] In formula (61), R ⁵⁸ and R ⁵⁹ are independently a fluorine atom or a trifluoromethyl group. Examples of diamine compounds that provide the structure of formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, and 4,4'-diaminooctafluorobiphenyl. These compounds may be used alone or in combination of two or more.

In addition, the following diamines can also be preferably used. [Chemical Formula 8]

R ¹¹⁵ in formula (2) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferred, and a group represented by the following formula (5) or formula (6) is more preferred. In formula (5) or formula (6), * independently represents a bonding site with other structures. [Chemical Formula 9] In formula (5), R ¹¹² is preferably a single bond or a group selected from aliphatic alkyl groups having 1 to 10 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S-, -SO ₂ - and -NHCO-, and combinations thereof; more preferably a single bond, a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted by fluorine atoms, -O-, -CO-, -S- and -SO ₂ -; and even more preferably a divalent group selected from the group consisting of -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- and -SO ₂ -.

Specifically, R ¹¹⁵ includes a tetracarboxylic acid residue remaining after removing anhydride groups from tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used. The tetracarboxylic dianhydride is preferably represented by the following formula (O). [Chemical Formula 10] In formula (O), R ¹¹⁵ represents a tetravalent organic group. The preferred range of R ¹¹⁵ is the same as that of R ¹¹⁵ in formula (2), and the preferred range is also the same.

Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylmethane tetracarboxylic dianhydride, 2,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,4,5,7-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6-naphthalenetetracarboxylic dianhydride, 2,2',3,3'-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and C1-6 alkyl and C1-6 alkoxy derivatives thereof.

Moreover, as a preferable example, tetracarboxylic dianhydride (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 can also be cited.

It is also preferred that at least one of R ¹¹¹ and R ¹¹⁵ has an OH group. More specifically, examples of R ¹¹¹ include a residual group of a diaminophenol derivative.

R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a monovalent organic group. It is preferred that at least one of R ¹¹³ and R ¹¹⁴ contains a polymerizable group, and it is more preferred that both contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, free radicals, etc., and a free radical polymerizable group is preferred. Specific examples of the polymerizable group include a group having an ethylenic unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxadiazole group, a blocked isocyanate group, a hydroxymethyl group, and an amine group. As the free radical polymerizable group possessed by a polyimide precursor, a group having an ethylenic unsaturated bond is preferred. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a group represented by the following formula (III). The group represented by the following formula (III) is preferred.

[Chemical formula 11]

In formula (III), R ²⁰⁰ represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In formula (III), * represents a bonding site with other structures. In formula (III), R ²⁰¹ represents an alkylene group having 2 to 12 carbon atoms, -CH ₂ CH (OH) CH ₂ -, or a polyalkylene group. Preferred examples of R ²⁰¹ include an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a 1,2-butanediyl group, a 1,3-butanediyl group, a pentamethylene group, a hexamethylene group, an octamethylene group, a dodecamethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group. An ethylene group, a propylene group, a trimethylene group, -CH ₂ CH (OH) CH ₂ -, and a polyalkylene group are more preferred, and a polyalkylene group is further preferred. In the present invention, a polyalkoxyl group refers to a group directly bonded with two or more alkoxyl groups. The alkylene groups in the plural alkoxyl groups contained in the polyalkoxyl group may be the same or different. When the polyalkoxyl group contains plural alkoxyl groups with different alkylene groups, the arrangement of the alkoxyl groups in the polyalkoxyl group may be a random arrangement, an arrangement with blocks, or an arrangement with alternating patterns. The carbon number of the above-mentioned alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, 2 to 10 is more preferred, 2 to 6 is more preferred, 2 to 5 is further preferred, 2 to 4 is further preferred, 2 or 3 is particularly preferred, and 2 is the best. In addition, the above-mentioned alkylene group may have a substituent. As preferred substituents, alkyl groups, aryl groups, halogen atoms, etc. can be cited. In addition, the number of alkoxy groups contained in the polyalkoxy group (the number of repetitions of the polyalkoxy group) is preferably 2 to 20, more preferably 2 to 10, and further preferably 2 to 6. As the polyalkoxy group, from the viewpoint of solvent solubility and solvent resistance, polyethoxy, polypropoxy, polytrimethyleneoxy, polytetramethyleneoxy or a group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups is preferred, polyethoxy or polypropoxy is more preferred, and polyethoxy is further preferred. In the group formed by bonding a plurality of ethoxy groups and a plurality of propoxy groups, the ethoxy groups and propoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in alternating patterns. The preferred aspects of the number of repetitions of the ethoxy groups and the like in these groups are as described above.

R ¹¹³ and R ¹¹⁴ are independently a hydrogen atom or a monovalent organic group. As the monovalent organic group, there can be mentioned an aromatic group and an aralkyl group having an acidic group bonded to one, two or three carbon atoms, preferably one of the carbon atoms constituting the aromatic group. Specifically, there can be mentioned an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, there can be mentioned a phenyl group having an acidic group and a benzyl group having an acidic group. The acidic group is preferably an OH group. It is also more preferred that R ¹¹³ or R ¹¹⁴ is a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group and a 4-hydroxybenzyl group.

From the viewpoint of solubility in organic solvents, R ¹¹³ or R ¹¹⁴ is preferably a monovalent organic group. The monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group. The number of carbon atoms in the alkyl group is preferably 1 to 30. The alkyl group may be any of a linear, branched, or cyclic group. Examples of the linear or branched alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy, 2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy, and 2-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy)ethoxy). The cyclic alkyl group may be a monocyclic or polycyclic cyclic alkyl group. Examples of monocyclic cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic cyclic alkyl groups include adamantyl, norbornyl, bornyl, camphenyl, decahydronaphthyl, tricyclodecyl, tetracyclodecyl, bornadiyl, bicyclohexyl, and pinenyl. Among them, cyclohexyl is the most preferred from the viewpoint of both high sensitivity and stability. In addition, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferred. The aromatic group may be specifically a substituted or unsubstituted benzene ring, a naphthyl ring, a pentadiene ring, an indene ring, an azulene ring, a heptadiene ring, an indenyl ring, a perylene ring, a condensed pentadiene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a condensed benzene ring, a chrysene ring, a tert-butylbenzene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyridine ring, a pyrrolidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, a pyrimidine ring, Indole ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinolyl ring, naphthidine ring, quinoline ring, quinazoline ring, isoquinoline ring, carbazole ring, phenanthidine ring, acridine ring, phenanthroline ring, thianthion ring, chromene ring, phenanthroline ring, phenanthrene ring, phenanthrene ring, phenanthrene ring, phenanthrene ring or phenanthrene ring. Benzene ring is the most preferred.

In formula (2), when R ¹¹³ is a hydrogen atom or when R ¹¹⁴ is a hydrogen atom, the polyimide precursor can form a conjugate with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

At least one of ^R113 and ^R114 may be a polar conversion group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is decomposed by an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and an acetal group is more preferred from the viewpoint of exposure sensitivity. Specific examples of the acid-decomposable group include a tert-butyloxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butyloxycarbonylmethyl group, a trimethylsilyl ether group, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.

In addition, the polyimide precursor preferably has fluorine atoms in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10 mass % or more, and preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, there can be mentioned an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like.

The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By setting such a structure, the width of the exposure latitude can be further expanded. Formula (2-A) [Chemical Formula 12] In formula (2-A), ^A1 and ^A2 represent oxygen atoms, ^R111 and ^R112 each independently represent a divalent organic group, ^R113 and ^R114 each independently represent a hydrogen atom or a monovalent organic group, at least one of ^R113 and ^R114 is a group containing a polymerizable group, and preferably both are polymerizable groups.

A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ are independently and independently the same as A ¹ , A ² , R ¹¹¹ , R ¹¹³ and R ¹¹⁴ in formula (2), and the preferred ranges are also the same. R ¹¹² is the same as R ¹¹² in formula (5), and the preferred ranges are also the same.

The polyimide precursor may contain one or more types of the repeating unit represented by formula (2). Furthermore, the polyimide precursor may contain structural isomers of the repeating unit represented by formula (2). Furthermore, the polyimide precursor may contain other types of repeating units in addition to the repeating unit represented by formula (2).

The polyimide precursor may include at least one repeating unit selected from the group consisting of repeating units represented by any one of the following formulae (2-1) to (2-6) as a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure. [Chemical Formula 13] In formula (2-1) to formula (2-6), R ¹¹¹ , R ¹¹³ , R ¹¹⁴ , R ¹¹⁵ , A ¹ and A ² have the same meanings as R ¹¹¹ , R ¹¹³ , R 114 , R ¹¹⁵ , A ¹ and A ² in the above formula (2 ⁾ , respectively, and preferred embodiments are also the same.

The total content of the repeating units represented by any one of formulae (2-1) to (2-6) is preferably an amount in which the total molar content of the cyclic imide structure and the cyclic isoimide structure in 1 g of the polyimide precursor is 0.08 to 1.68 mmol/g. The total molar content is more preferably 0.10 to 1.00 mmol/g, further preferably 0.12 to 0.80 mmol/g, and particularly preferably 0.15 to 0.60 mmol/g.

As an embodiment of the polyimide precursor of the present invention, the content of the repeating unit represented by formula (2) is 50 mol% or more of all the repeating units. The total content is preferably 70 mol% or more, more preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular limitation on the upper limit of the total content, except that all the repeating units in the terminal polyimide precursor can be any of the repeating units represented by formula (2) and any of the repeating units represented by formulas (2-1) to (2-6).

The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and further preferably 22,000 to 25,000. Moreover, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more. The upper limit of the molecular weight dispersion of the polyimide precursor is not particularly specified, for example, 4.5 or less is preferred, 4.0 or less is more preferred, 3.8 or less is further preferred, 3.2 or less is further preferred, 3.1 or less is further preferred, 3.0 or less is further preferred, and 2.95 or less is particularly preferred. In this specification, the molecular weight dispersion is a value calculated using weight average molecular weight/number average molecular weight.

[Polybenzoxazole precursor] The structure of the polybenzoxazole precursor used in the present invention is not particularly limited, but preferably comprises a repeating unit represented by the following formula (3). [Chemical formula 14] In formula (3), ^R121 represents a divalent organic group, ^R122 represents a tetravalent organic group, and ^R123 and ^R124 each independently represent a hydrogen atom or a monovalent organic group.

In formula (3), R ¹²³ and R ¹²⁴ are synonymous with R ¹¹³ in formula (2), and the preferred ranges are also the same. That is, it is preferred that at least one of them is a polymerizable group. In formula (3), R ¹²¹ represents a divalent organic group. As the divalent organic group, a group containing at least one of an aliphatic group and an aromatic group is preferred. As the aliphatic group, a straight-chain aliphatic group is preferred. It is preferred that R ¹²¹ is a dicarboxylic acid residue. Only one dicarboxylic acid residue may be used, or two or more dicarboxylic acid residues may be used.

As the dicarboxylic acid residue, dicarboxylic acids containing aliphatic groups and dicarboxylic acid residues containing aromatic groups are preferred, and dicarboxylic acid residues containing aromatic groups are more preferred. As the dicarboxylic acid containing aliphatic groups, dicarboxylic acids containing linear or branched (preferably linear) aliphatic groups are preferred, and dicarboxylic acids composed of linear or branched (preferably linear) aliphatic groups and 2 -COOH groups are more preferred. The carbon number of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, further preferably 3 to 20, further preferably 4 to 15, and particularly preferably 5 to 10. The linear aliphatic group is preferably an alkylene group. As dicarboxylic acids containing a linear aliphatic group, there can be mentioned malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, behenedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, triacontanedioic acid, diglycolic acid acid) and the dicarboxylic acid represented by the following formula, etc.

[Chemical formula 15] (In the formula, Z is a carbonyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 6.)

As the dicarboxylic acid containing an aromatic group, the following dicarboxylic acids having an aromatic group are preferred, and the following dicarboxylic acids consisting only of an aromatic group and two -COOH groups are more preferred.

[Chemical formula 16] In the formula, A represents a divalent group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, -C(CF ₃ ) ₂ -, and -C(CH ₃ ) ₂ -, and * represents a bonding site with other structures independently.

Specific examples of the dicarboxylic acid containing an aromatic group include 4,4'-carbonyldibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.

In formula (3), R ¹²² represents a tetravalent organic group. The tetravalent organic group has the same meaning as R ¹¹⁵ in formula (2), and the preferred range is also the same. The group ¹²² derived from a diaminophenol derivative is also preferred. Examples of the group derived from a diaminophenol derivative include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxydiphenylsulfone, bis-(3-amino-4-hydroxyphenyl)methane, 2,2-bis-(3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl)hexafluoropropane, bis-(4-amino-3-hydroxyphenyl)methane, 2,2-bis-(4-amino-3-hydroxyphenyl)propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 1,3-diamino-4,6-dihydroxybenzene, etc. Such bisaminophenols can be used alone or in combination.

Among the diaminophenol derivatives, the following diaminophenol derivatives having an aromatic group are preferred.

[Chemical formula 17] In the formula, _X1 represents -O-, -S-, -C( _CF3 ) _2- , _-CH2- , _-SO2- , -NHCO-, and * and # represent the bonding site with other structures. R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a alkyl group, and more preferably a hydrogen atom or an alkyl group. In addition, ^R122 is also preferably a structure represented by the above formula. When R ¹²² is a structure represented by the above formula, any two of the four * and # in total are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the other two are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is preferred that the two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, or the two * are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded, and the two # are bonding sites to the oxygen atom to which R 122 in formula (3) is bonded. It is more preferred that the two * are bonding sites to the oxygen atom to which R ¹²² in formula (3) is bonded. It is further preferred that the two #s are bonding sites to the oxygen atom to which ^{R 122} is bonded, and the two #s are bonding sites to the nitrogen atom to which R ¹²² in formula (3) is bonded.

[Chemical formula 18]

In formula (As), _R1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, _-SO2- , -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). _R2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different. _R3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and they may be the same or different.

[Chemical formula 19] (In formula (A-sc), * represents an aromatic ring bonded to the aminophenol group of the bisaminophenol derivative represented by the above formula (As).)

In the above formula (As), it is particularly preferred to have a substituent at _R3 adjacent to the phenolic hydroxyl group because the carbonyl carbon of the amide bond and the hydroxyl group are closer together, thereby further improving the effect of achieving a high cyclization rate during curing at a low temperature.

In the above formula (As), when R ₂ and R ₃ are both alkyl groups, it is preferred because high transparency to I-rays and high cyclization rate during curing at low temperatures can be maintained.

In the above formula (As), _R1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group for _R1 include a linear or branched alkyl group having 1 to 8 carbon atoms. Among them, -CH2-, -CH(CH3)-, and -C( _CH3 ) _2- are more preferred from the viewpoint of obtaining a polybenzoxazole precursor having an excellent balance of maintaining high transparency to I- _rays and high cyclization rate _when curing at low temperature and having sufficient solubility in solvents.

For a method for producing the bisaminophenol derivative represented by the above formula (A-s), reference may be made to, for example, paragraphs 0085 to 0094 and Example 1 (paragraphs 0189 to 0190) of Japanese Patent Application Laid-Open No. 2013-256506, the contents of which are incorporated herein.

Specific examples of the structure of the bisaminophenol derivative represented by the above formula (A-s) include those described in paragraphs 0070 to 0080 of JP-A-2013-256506, and the contents thereof are incorporated into the present specification. However, the present invention is not limited to these.

The polybenzoxazole precursor may contain other types of repeating structural units in addition to the repeating units of the above formula (3). As the repeating units having a benzoxazole structure, the polybenzoxazole precursor may contain at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (3-1), a repeating unit represented by the following formula (3-2), and a repeating unit represented by the following formula (3-3). [Chemical Formula 20] In formula (3-1) to formula (3-3), R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ have the same meanings as R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ in formula (3), respectively, and preferred embodiments are also the same.

The content of the repeating unit represented by formula (3-1), the repeating unit represented by formula (3-2), and the repeating unit represented by formula (3-3) is preferably such that the molar content of the benzoxazole structure in 1 g of the polybenzoxazole precursor is 0.22 to 3.97 mmol/g. The molar content is more preferably 0.25 to 3.00 mmol/g, further preferably 0.28 to 2.50 mmol/g, and particularly preferably 0.30 to 2.00 mmol/g.

Furthermore, from the viewpoint of being able to suppress the occurrence of warp associated with ring closure, the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating structural unit.

[Chemical formula 21] In formula (SL), Z has structure a and structure b, R ^1s is a hydrogen atom or a alkyl group having 1 to 10 carbon atoms, R ^2s is a alkyl group having 1 to 10 carbon atoms, at least one of R ^3s , R ^4s , R ^5s , and R ^6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different. The polymerization of structure a and structure b may be block polymerization or random polymerization. Regarding the molar % of the Z portion, structure a is 5 to 95 molar %, structure b is 95 to 5 molar %, and a+b is 100 molar %.

In formula (SL), as preferred Z, R ^5s and R ^6s in structure b are phenyl groups. In addition, the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, and more preferably 500 to 3,000. By setting the molecular weight within the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be more effectively reduced, and the effect of suppressing warp and the effect of improving solvent solubility can be taken into account.

When the diamine residue represented by formula (SL) is included as another type of repeating structural unit, it is also preferred to further include a tetracarboxylic acid residue remaining after removing the anhydride group from tetracarboxylic dianhydride as a repeating structural unit. As an example of such a tetracarboxylic acid residue, R ¹¹⁵ in formula (2) can be cited.

For example, when the polybenzoxazole precursor is used in the composition described below, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 to 30,000, more preferably 20,000 to 29,000, and further preferably 22,000 to 28,000. In addition, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and further preferably 9,200 to 11,200. The molecular weight dispersion of the above polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersion of the polybenzoxazole precursor is not particularly specified, but is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and even more preferably 2.2 or less.

[Polyamide imide precursor] The polyamide imide precursor preferably comprises a repeating unit represented by the following formula (PAI-2). [Chemical Formula 22] In formula (PAI-2), R ¹¹⁷ represents a trivalent organic group, R ¹¹¹ represents a divalent organic group, A ² represents an oxygen atom or -NH-, and R ¹¹³ represents a hydrogen atom or a monovalent organic group.

In formula (PAI-2), R ¹¹⁷ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group formed by linking two or more of them via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of them via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of them, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of them. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and further preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be cited, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be cited. As the above-mentioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

Furthermore, R ¹¹⁷ is preferably derived from a tricarboxylic acid compound in which at least one carboxyl group can be halogenated. As the above-mentioned halogenation, chlorination is preferred. In the present invention, a compound having three carboxyl groups is referred to as a tricarboxylic acid compound. Two of the three carboxyl groups of the above-mentioned tricarboxylic acid compound can be anhydrided. As the tricarboxylic acid compound that can be halogenated used in the preparation of the polyamide imide precursor, branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds can be cited. Such tricarboxylic acid compounds can be used alone or in combination of two or more.

Specifically, as the tricarboxylic acid compound, a tricarboxylic acid compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group is preferred, and a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

Specific examples of tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, phthalic acid (or phthalic anhydride) and benzoic acid, compounds linked by a single bond, -O-, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or phenylene group, etc. These compounds may be compounds in which two carboxyl groups are anhydrified (e.g., trimellitic anhydride) or compounds in which at least one carboxyl group is halogenated (e.g., trimellitic anhydride acyl chloride).

In the formula (PAI-2), R ¹¹¹ , A ² , and R ¹¹³ have the same meanings as R ¹¹¹ , A ² , and R ¹¹³ in the above formula (2), and preferred embodiments thereof are also the same.

The polyamide imide precursor may also contain other repeating units. Examples of other repeating units include the repeating units represented by the above formula (2), the repeating units represented by the formula (2-1), the repeating units represented by the formula (2-2), the repeating units represented by the formula (2-3), and the repeating units represented by the following formula (PAI-1). [Chemical Formula 23]

In formula (PAI-1), R ¹¹⁶ represents a divalent organic group, and R ¹¹¹ represents a divalent organic group. In formula (PAI-1), R ¹¹⁶ can be exemplified by a linear or branched aliphatic group, a cyclic aliphatic group and an aromatic group, a heteroaromatic group, or a group in which two or more of these are linked via a single bond or a linking group. Preferably, it is a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group. More preferably, it is an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined via a single bond or a linking group. The linking group is preferably -O-, -S-, -C(=O)-, -S(=O) _2- , an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of them, and more preferably -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group formed by bonding two or more of them. The alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and further preferably an alkylene group having 1 to 4 carbon atoms. The halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and further preferably a halogenated alkylene group having 1 to 4 carbon atoms. In addition, as the halogen atom in the above-mentioned halogenated alkylene group, fluorine atom, chlorine atom, bromine atom, iodine atom and the like can be cited, and fluorine atom is preferred. The above-mentioned halogenated alkylene group may have a hydrogen atom, or all hydrogen atoms may be substituted by halogen atoms, but all hydrogen atoms are preferably substituted by halogen atoms. As examples of preferred halogenated alkylene groups, (ditrifluoromethyl)methylene and the like can be cited. As the above-mentioned arylene group, phenylene or naphthylene is preferred, phenylene is more preferred, and 1,3-phenylene or 1,4-phenylene is further preferred.

Furthermore, R ¹¹⁶ is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound. In the present invention, a compound having two carboxyl groups is referred to as a dicarboxylic acid compound, and a compound having two halogenated carboxyl groups is referred to as a dicarboxylic acid dihalide compound. The carboxyl groups in the dicarboxylic acid dihalide compound may be halogenated, but are preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound. As the dicarboxylic acid compound or dicarboxylic acid dihalide compound that can be halogenated and is used in the production of the polyamide imide precursor, there can be cited linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acid dihalide compounds, etc. Only one kind of the dicarboxylic acid compound or the dihalide dicarboxylic acid compound may be used, or two or more kinds may be used.

Specifically, as the dicarboxylic acid compound or dicarboxylic acid dihalide compound, a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more of these groups via a single bond or a linking group is preferred, and a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing an aromatic group having 6 to 20 carbon atoms, or a group formed by combining two or more aromatic groups having 6 to 20 carbon atoms via a single bond or a linking group is more preferred.

Specific examples of the dicarboxylic acid compound include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid Monoacanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacanedioic acid, nonacosanedioic acid, triacontanedioic acid, triacontanedioic acid, docosanedioic acid, diglycolic acid acid), phthalic acid, isophthalic acid, terephthalic acid, 4,4’-biphenylcarboxylic acid, 4,4’-dicarboxyldiphenyl ether, benzophenone-4,4’-dicarboxylic acid, etc. Specific examples of the dicarboxylic acid dihalide compound include compounds having a structure in which two carboxyl groups are halogenated among the specific examples of the above-mentioned dicarboxylic acid compounds.

In formula (PAI-1), R ¹¹¹ has the same meaning as R ¹¹¹ in the above formula (2), and the preferred embodiment is also the same.

The polyamide imide precursor may include a repeating unit having at least one of a cyclic imide structure and a cyclic isoimide structure, and may include a repeating unit represented by any one of the following formulas (PAI-3) and (PAI-4). [Chemical Formula 24] In formula (PAI-3) or formula (PAI-4), R ¹¹¹ and R ¹¹⁷ have the same meanings as R ¹¹¹ and R ¹¹⁷ in formula (PAI-2), respectively, and preferred embodiments are also the same.

The content of the repeating unit represented by any one of the formulae (PAI-3) and (PAI-4) is preferably such that the total content of the cyclic imide structure and the cyclic isoimide structure in the polyamide imide precursor is 0.062 to 1.186 mmol/g. The total content is more preferably 0.070 to 1.000 mmol/g, further preferably 0.080 to 0.800 mmol/g, and particularly preferably 0.090 to 0.700 mmol/g.

In addition, the polyamide imide preferably has fluorine atoms in the structural unit. The fluorine atom content in the polyamide imide precursor is preferably 10 mass % or more, and preferably 20 mass % or less.

In order to improve the adhesion to the substrate, the polyamide imide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, as the diamine component, there can be mentioned an embodiment in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, and the like are used.

As an embodiment of the polyamide imide precursor of the present invention, there can be cited an aspect in which the total content of the repeating unit represented by the formula (PAI-2), the repeating unit represented by the formula (PAI-1), the repeating unit represented by the formula (PAI-3), the repeating unit represented by the formula (PAI-4), the repeating unit represented by the formula (2), and the repeating unit represented by any one of the formulas (2-1) to (2-6) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit on the above-mentioned total content, except that all repeating units in the terminal polyamide imide precursor can be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), the repeating units represented by any one of formulas (PAI-3) and (PAI-4), the repeating units represented by formula (2), and the repeating units represented by any one of formulas (2-1) to (2-6). In addition, as another embodiment of the polyamide imide precursor in the present invention, there can be cited an embodiment in which the total content of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), and the repeating units represented by any one of formulas (PAI-3) and (PAI-4) is 50 mol% or more of all the repeating units. The total content is more preferably 70 mol% or more, further preferably 90 mol% or more, and particularly preferably more than 90 mol%. There is no particular upper limit on the total content, except that all repeating units in the terminal polyamide imide precursor may be any of the repeating units represented by formula (PAI-2), the repeating units represented by formula (PAI-1), or the repeating units represented by any of formulas (PAI-3) and (PAI-4).

The weight average molecular weight (Mw) of the polyamide imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and further preferably 4,000 to 25,000.

The molecular weight dispersion of the polyamide imide precursor is preferably 1.5 to 3.5, and more preferably 2 to 3. In this specification, the molecular weight dispersion refers to the value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight/number average molecular weight).

[Production method of polyimide precursor, etc.] Polyimide precursor, etc. is obtained by reacting dicarboxylic acid or dicarboxylic acid derivative with diamine. It is preferably obtained by halogenating dicarboxylic acid or dicarboxylic acid derivative with diamine using a halogenating agent. In the production method of polyimide precursor, etc., it is preferred to use an organic solvent when performing the reaction. The organic solvent may be one or more. As the organic solvent, it can be appropriately specified according to the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether), N-methylpyrrolidone and N-ethylpyrrolidone.

Furthermore, it is also preferable to use a non-halogen catalyst for synthesis instead of the above-mentioned halogenating agent. As the above-mentioned non-halogen catalyst, a known amidation catalyst that does not contain a halogen atom can be used without particular limitation, for example, boroxine compounds, N-hydroxy compounds, tertiary amines, phosphates, amine salts, urea compounds, carbodiimide compounds, etc. can be cited. As the above-mentioned carbodiimide compound, N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, etc. can be cited. In the production method of polyimide precursors, it is preferable to use an organic solvent when performing the reaction. The organic solvent can be one or more. The organic solvent can be appropriately specified depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.

-Capping agent- In the production method of polyimide precursors, in order to further improve storage stability, it is preferred to seal the ends of polyimide precursors with a capping agent such as anhydride, monocarboxylic acid, monoacyl chloride compound, monoactive ester compound, etc. As the end-capping agent, it is more preferable to use a monoamine. As preferred compounds of the monoamine, there can be cited aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy- 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, etc. Two or more of these can be used, and by reacting a plurality of end-capping agents, a plurality of different terminal groups can be introduced.

-Solid precipitation- When manufacturing a polyimide precursor, a process for solid precipitation may be included. Specifically, the polyimide precursor in the reaction solution is precipitated in water and dissolved in a solvent such as tetrahydrofuran in which the polyimide precursor is soluble, thereby allowing solid precipitation. Then, the polyimide precursor is dried to obtain a powdered polyimide precursor.

[Content] The content of the specific resin in the composition of the present invention is preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, and 50% by mass or more relative to the total solid content of the composition. In addition, the content of the resin in the composition of the present invention is preferably 99.5% by mass or less, 99% by mass or less is more preferably, 98% by mass or less is more preferably, 97% by mass or less is more preferably, and 95% by mass or less is more preferably relative to the total solid content of the composition. The composition of the present invention may contain only one specific resin or two or more. When containing two or more, it is preferred that the total amount be within the above range.

Furthermore, the curable resin composition of the present invention preferably contains at least two resins. Specifically, the curable resin composition of the present invention may contain two or more specific resins and other resins described below in total, or may contain two or more specific resins, but it is preferred to contain two or more specific resins. When the curable resin composition of the present invention contains two or more specific resins, for example, it is preferred to contain two or more polyimide precursors having different structures (R ¹¹⁵ in the above formula (2)) derived from polyimide precursors.

<Specific compound> The curable resin composition of the present invention comprises at least one (specific compound) selected from the group consisting of compounds represented by formula (1-1), compounds represented by formula (1-2) and compounds represented by formula (1-3). [Chemical formula 25] In formula (1-1), formula (1-2) or formula (1-3), ^R11 and ^R12 each independently represent an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, an aliphatic alkyl group having 1 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure, a quaternary ammonium group and an aliphatic heterocyclic group, or an aliphatic alkyl group having 2 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group and an alkylthio group, ^R21 and ^R22 each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, ^R31 and ^R32 each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.

[R ¹¹ and R ¹² ] In formula (1-1), R ¹¹ and R ¹² are each independently an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms having as a substituent at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure and a quaternary ammonium group. An unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred. As the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in ^R11 and ^R12 , an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is preferred, an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms is more preferred, and ethyl, isopropyl, t-butyl or cyclohexyl is more preferred.

As the substituent in ^R11 and ^R12 , an aliphatic alkyl group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure, a quaternary ammonium group, and an aliphatic heterocyclic group, preferably a saturated aliphatic alkyl group having 1 to 7 carbon atoms having the above substituent. The above aliphatic alkyl group may have a plurality of the above substituents, but preferably has only one of the above substituents.

The primary amine salt structure in the above substituent refers to a salt structure including a primary amine group (-NH ₂ ) and an acid, preferably a salt structure including a primary amine group and an inorganic acid, and examples thereof include a hydrochloride structure. The secondary amine salt structure in the above substituent refers to a salt structure including a secondary amine group (-NRH, R represents an organic group) and an acid, preferably a salt structure including a secondary amine group and an inorganic acid, and examples thereof include a hydrochloride structure. The secondary amine group constituting the secondary amine salt structure in the above substituent includes a monoalkylamine group, a monoarylamine group, and the like, and preferably a monoalkylamine group having 1 to 4 carbon atoms. The tertiary amine salt structure in the above substituent refers to a salt structure including a tertiary amine group ( _-NR2 , R each independently represents an organic group) and an acid, and the salt structure of the tertiary amine group and an inorganic acid is preferred, and hydrochloride salt structure can be cited. As the tertiary amine group in the above substituent or the tertiary amine constituting the tertiary amine, a dialkylamine group is preferred, and a dialkylamine group in which the carbon numbers of the two alkyl groups are independently 1 to 4 is more preferred, and a dimethylamine group is more preferred. In addition, when one of ^R11 and ^R12 has any one of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, and a tertiary amine salt structure as a substituent, the other of ^R11 and ^R12 is preferably the above unsubstituted aliphatic alkyl group having 1 to 7 carbon numbers. As a substituent, an aliphatic hydrocarbon group having 1 to 7 carbon atoms selected from at least one of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group and a tertiary amine salt structure is provided. Preferably, a straight-chain or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms with the substituent is provided at the terminal. More preferably, a straight-chain or branched saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms with the substituent is provided at the terminal. Further preferably, a straight-chain saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms with the substituent is provided at the terminal.

As the quaternary ammonium group in the above substituent, the group represented by the following formula (A-1) is preferred. [Chemical Formula 26] In formula (A-1), R ^A1 to R ^A3 each independently represent a alkyl group, at least two of R ^A1 to R ^A3 can bond to form a ring structure, X represents a relative anion, and * represents a bonding site with an aliphatic alkyl group having 1 to 7 carbon atoms. In formula (A-1), R ^A1 to R ^A3 each independently represent an aromatic alkyl group or an alkyl group, more preferably a phenyl group or an alkyl group having 1 to 4 carbon atoms, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. The embodiment in which all of R ^A1 to R ^A3 are methyl groups is also one of the preferred embodiments of the present invention. Examples of the ring structure formed by at least two of ^RA1 to ^RA3 being bonded include saturated aliphatic hydrocarbon rings such as cyclohexyl ring, unsaturated aliphatic hydrocarbon rings such as cyclohexene ring, and saturated aliphatic heterocyclic rings such as morpholine ring. In formula (A-1), X represents a relative anion, which may be a monovalent anion or a divalent or higher anion, but a monovalent anion is preferred. Furthermore, X is not particularly limited, but a halogenide ion or a toluenesulfonic acid anion is preferred, and a halogenide ion is more preferred. As the above-mentioned halogenide ions, there can be cited fluoride ions, salt ions, ozone ions, iodide ions, etc., and salt ions are preferred. In addition, when one of R ¹¹ and R ¹² has a quaternary ammonium group as a substituent, the other of R ¹¹ and R ¹² is preferably the above-mentioned unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. The aliphatic hydrocarbon group having 1 to 7 carbon atoms and having a quaternary ammonium group as a substituent is preferably a linear or branched saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms and having a quaternary ammonium group at the terminal, more preferably a linear or branched saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms and having a quaternary ammonium group at the terminal, and even more preferably a linear saturated aliphatic hydrocarbon group having 3 to 5 carbon atoms and having a quaternary ammonium group at the terminal.

As the hetero atom in the aliphatic heterocyclic group in the above-mentioned substituent, oxygen atom, nitrogen atom, sulfur atom, etc. can be cited, and oxygen atom is preferred. The above-mentioned aliphatic heterocyclic group may have only one hetero atom, or may have two or more. The above-mentioned aliphatic heterocyclic group is preferably a 5-membered ring structure or a 6-membered ring structure, and a 5-membered ring structure is more preferred. The above-mentioned aliphatic heterocyclic group may further have a known substituent such as an alkyl group. As the above-mentioned aliphatic heterocyclic group, 2,2-dimethyl-1,3-dioxolane-4-yl is preferred. When one of R ¹¹ and R ¹² has an aliphatic heterocyclic group as a substituent, the other of R ¹¹ and R ¹² preferably has an aliphatic heterocyclic group as a substituent. The aliphatic alkyl group having 1 to 7 carbon atoms and having an aliphatic heterocyclic group as a substituent is preferably a saturated aliphatic alkyl group having 1 to 7 carbon atoms and having an aliphatic heterocyclic group at the terminal, more preferably a linear or branched saturated aliphatic alkyl group having 1 to 4 carbon atoms and having an aliphatic heterocyclic group at the terminal, and even more preferably a methyl group having an aliphatic heterocyclic group.

R ¹¹ and R ¹² may each independently be an aliphatic alkyl group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group. The aliphatic alkyl group having 2 to 7 carbon atoms may have two or more of the substituents, but an aspect having only one of the substituents is also one of the preferred aspects of the present invention. As the alkoxy group, an alkoxy group having 1 to 10 carbon atoms is preferred, and an alkoxy group having 1 to 4 carbon atoms is more preferred. As the alkylthio group, an alkylthio group having 1 to 10 carbon atoms is preferred, and an alkylthio group having 1 to 4 carbon atoms is more preferred. As the aliphatic alkyl group having 2 to 7 carbon atoms, a saturated aliphatic alkyl group having 2 to 7 carbon atoms is preferred, and a saturated aliphatic alkyl group having 2 to 4 carbon atoms is more preferred. Examples of the aliphatic alkyl group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group, and an alkylthio group include, but are not limited to, a hydroxyethyl group, a hydroxypropyl group, a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group, an ethoxypropyl group, and the like.

[R ²¹ and R ²² ] R ²¹ and R ²² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent. R ²¹ and R ²² are preferably an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, or an aliphatic alkyl group having ¹ to 7 carbon atoms which has an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms. Preferred embodiments of the unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, or the aliphatic alkyl group having 1 to 7 carbon atoms which has the above substituent in R ²¹ and R 22 are the same as those described in the description of R ¹¹ and R ¹² , respectively.

[R ³¹ and R ³² ] R ³¹ and R ³² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent. R ³¹ and R ³² are preferably an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms or an aliphatic alkyl group having 1 to 7 carbon atoms which has an amino group or a ^quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms. Preferred embodiments of the unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms or the aliphatic alkyl group having 1 to 7 carbon atoms which has the above substituent in R ³¹ and R 32 are the same as those described in the description of R ¹¹ and R ¹² , respectively.

[R ³³ ] R ³³ represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. R ³³ is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, and more preferably an ethyl group.

From the perspective of resolution, the content of the specific compound relative to the total mass of the curable resin composition is 10 to 50,000 ppm, preferably 30 to 20,000 ppm, and even more preferably 70 to 15,000 ppm. When the curable resin composition contains two or more specific compounds, the above content is the total mass of all the specific compounds.

Furthermore, the specific compound is preferably a compound that does not contain a free radical polymerizable group such as an ethylenic unsaturated group, an epoxy group, an oxycyclobutyl group, an alkoxyalkyl group, a hydroxyalkyl group, an alkoxysilyl group, and a silanol group.

As specific examples of the specific compound, there are no particular limitations, and compounds represented by formula (G-1) to formula (G-27) used in the embodiments described below can be cited. Among them, from the perspective of resolution, the compound represented by any one of formula (G-1) to formula (G-12) is preferred.

<Organic metal complex> The curable resin composition of the present invention contains an organic metal complex. The organic metal complex may be any organic complex compound containing a metal atom, but a complex compound containing a metal atom and an organic group is preferred, a complex compound in which an organic group is coordinated to a metal atom is more preferred, and a metallocene compound is further preferred. In the present invention, a metallocene compound refers to an organic metal complex having two cyclopentadienyl derivatives which may have substituents as η5-ligands. The organic group is not particularly limited, and a group consisting of a alkyl group or a combination of an alkyl group and a heteroatom is preferred. As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferred. In the present invention, at least one of the organic groups is preferably a cyclic group, and at least two are more preferably cyclic groups. The cyclic group is preferably selected from a cyclic group with five members and a cyclic group with six members, and a cyclic group with five members is more preferably. The cyclic group may be a hydrocarbon ring or a heterocyclic ring, but a hydrocarbon ring is preferred. As a cyclic group with five members, a cyclopentadienyl group is preferred. In addition, the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.

The metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to the Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium and einsteinium, further preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.

The organometallic complex may contain two or more metal atoms, or may contain one metal atom, but preferably contains one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one metal atom, or may contain two or more metal atoms.

The organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.

The aspect in which the organometallic complex has the ability to initiate photo-radical polymerization is also one of the preferred aspects of the present invention. According to the present invention, it is believed that by using a specific resin, the organometallic complex is dispersed in a nearly uniform state in the film. Therefore, it is believed that when the organometallic complex has the ability to initiate photo-radical polymerization, the aggregation of local radical polymerization initiators caused by the aggregation of the organometallic complex can be suppressed. It is believed that by suppressing the aggregation of radical polymerization initiators, the degree of polymerization of the specific resin or crosslinking agent in the film is also likely to become nearly uniform. Therefore, it is believed that the generation of development residues, broken lines of patterns, etc. are unlikely to occur, and the resolution is likely to be improved. In the present invention, having the ability to initiate photo-radical polymerization means that free radicals capable of initiating free radical polymerization can be generated by irradiation with light. For example, when a composition comprising a free radical crosslinking agent and an organic metal complex is irradiated with light in a wavelength region where the organic metal complex absorbs light and the free radical crosslinking agent does not absorb light, the presence or absence of the ability to initiate photo-radical polymerization can be confirmed by confirming the disappearance of the free radical crosslinking agent. When confirming the disappearance, an appropriate method can be selected according to the type of free radical crosslinking agent, such as by IR measurement (infrared spectrometry) or HPLC measurement (high performance liquid chromatography). When the organic metal complex has the ability to initiate photo-radical polymerization, the organic metal complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a bismuthocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound. When the organometallic complex does not have photo-radical polymerization initiation energy, the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxy titanium compounds, acylated titanium compounds, chelated titanium compounds, zirconocene compounds and mesocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and mesocene compounds, further preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably titanocene compounds.

The molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.

As an organometallic complex, a compound represented by the following formula (P) can be cited. [Chemical Formula 27] In formula (P), M is a metal atom, and R is independently a substituent. Preferably, the R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.

In formula (P), as the metal atom represented by M, iron atom, titanium atom, zirconium atom or eurium atom is preferred, titanium atom, zirconium atom or eurium atom is more preferred, titanium atom or zirconium atom is further preferred, and titanium atom is particularly preferred. As the aromatic group in R in formula (P), aromatic groups having 6 to 20 carbon atoms, aromatic alkyl groups having 6 to 20 carbon atoms are preferred, phenyl, 1-naphthyl or 2-naphthyl, etc. can be cited. As the alkyl group in R in formula (P), alkyl groups having 1 to 20 carbon atoms are preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and methyl, ethyl, propyl, octyl, isopropyl, t-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be cited. As the halogen atom in the above R, F, Cl, Br, and I can be cited. As the alkyl group constituting the alkylsulfonyloxy group in the above R, an alkyl group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 10 carbon atoms is more preferred, and methyl, ethyl, propyl, octyl, isopropyl, t-butyl, isopentyl, 2-ethylhexyl, 2-methylhexyl, cyclopentyl, etc. can be cited. The above R may also have a substituent. As examples of the substituent, halogen atoms (F, Cl, Br, I), hydroxyl, carboxyl, amino, cyano, aryl, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, monoalkylamino, dialkylamino, monoarylamino, and diarylamino can be cited.

Specific examples of the organometallic complex are not particularly limited, and examples thereof include tetraisopropoxytitanium, tetra(2-ethylhexyloxy)titanium, diisopropoxybis(ethyl acetylacetate)titanium, diisopropoxybis(acetylacetone)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltrimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds. [Chemical Formula 28]

In addition, the compounds described in paragraphs 0078 to 0088 of International Publication No. 2018/025738 can also be used, but are not limited thereto.

The content of the organometallic complex is preferably 0.1 to 30 mass % relative to the total solid content of the curable resin composition of the present invention. The lower limit is preferably 1.0 mass % or more, 1.5 mass % or more is further preferably, and 3.0 mass % or more is further preferably. The upper limit is preferably 25 mass % or less. One or more organometallic complexes can be used. When two or more are used, the total amount is preferably within the above range.

<Other resins> The composition of the present invention may contain the above-mentioned specific resin and other resins different from the specific resin (hereinafter, also referred to as "other resins"). As other resins, polyamide imide, polyamide imide precursor, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, acrylic resin, etc. can be cited. For example, by further adding an acrylic resin, a composition with excellent coating properties can be obtained, and an organic film with excellent solvent resistance can be obtained. For example, by adding a highly polymerizable acrylic resin having a weight average molecular weight of 20,000 or less to the composition instead of or in addition to the crosslinking agent described below, the coating properties of the composition and the solvent resistance of the organic film can be improved.

When the composition of the present invention contains other resins, the content of the other resins relative to the total solid content of the composition is preferably 0.01 mass% or more, 0.05 mass% or more is more preferably, 1 mass% or more is further preferably, 2 mass% or more is further preferably, 5 mass% or more is further preferably, and 10 mass% or more is further preferably. In addition, the content of the other resins in the composition of the present invention relative to the total solid content of the composition is preferably 80 mass% or less, 75 mass% or less is more preferably, 70 mass% or less is further preferably, 60 mass% or less is further preferably, and 50 mass% or less is further preferably. In addition, as a preferred embodiment of the composition of the present invention, the content of other resins can also be set to a low content. In the above embodiment, the content of other resins relative to the total solid content of the composition is preferably 20% by mass or less, 15% by mass or less is more preferred, 10% by mass or less is further preferred, 5% by mass or less is further preferred, and 1% by mass or less is further preferred. The lower limit of the above content is not particularly limited, as long as it is 0% by mass or more. The composition of the present invention may contain only one other resin, or may contain two or more. When containing two or more, it is preferred that the total amount be within the above range.

<Solvent> The curable resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfones, amides, ureas, and alcohols.

As esters, preferred examples include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3- ethyl ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.

As ethers, preferred ones include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiourea acetate, ethyl thiourea acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate and the like.

As ketones, preferred examples include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosan, and dihydrolevoglucosan.

Preferred examples of the cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

As the sulfoxides, dimethyl sulfoxide is preferably mentioned.

As the amides, preferred ones include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.

As the urea, preferably, N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like can be cited.

As alcohols, there can be cited methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylbenzyl alcohol, n-pentanol, methylpentanol and diacetone alcohol.

From the viewpoint of improving the properties of the coated surface, it is also preferred that the solvent is in the form of a mixture of two or more solvents.

In the present invention, a solvent selected from 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, ethyl celulose acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, 3-methoxypropionic acid methyl ester, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether and propylene glycol methyl ether acetate, or a mixed solvent consisting of two or more of the solvents is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone is particularly preferred. In addition, the combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and γ-butyrolactone is also preferred.

From the viewpoint of coating properties, the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80 mass %, more preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 75 mass %, more preferably such that the total solid content concentration of the curable resin composition of the present invention is 10 to 70 mass %, and even more preferably such that the total solid content concentration of the curable resin composition of the present invention is 40 to 70 mass %. The content of the solvent may be adjusted according to the required thickness of the coating film and the coating method.

The solvent may contain only one kind or two or more kinds. When two or more kinds of solvents are contained, it is preferred that the total amount of the solvents is within the above range.

<Photosensitive agent> The composition of the present invention preferably contains a photosensitive agent. The photosensitive agent does not contain the above-mentioned organometallic complex and a compound having the ability to initiate photo-radical polymerization. The composition of the present invention preferably contains a photopolymerization initiator.

[Photopolymerization initiator] In the composition of the present invention, it is preferred to include a photopolymerization initiator as a photosensitizer. The photopolymerization initiator is preferably a photoradical polymerization initiator. There is no particular limitation on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet region to the visible region is preferred. In addition, it can also be an activator that generates active radicals by reacting with a photoexcited sensitizer in some way.

In the present invention, the compound corresponding to the organometallic complex does not correspond to the photosensitizer and the photo-radical polymerization initiator.

When the organometallic complex has the ability to initiate photo-radical polymerization, it is also preferred that the composition of the present invention does not actually contain a radical polymerization initiator other than the above-mentioned organometallic complex. Substantially not containing a radical polymerization initiator other than the above-mentioned organometallic complex means that in the composition of the present invention, the content of other radical polymerization initiators other than the above-mentioned organometallic complex is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass, relative to the total mass of the above-mentioned organometallic complex. In addition, when the composition of the present invention contains an organometallic complex having the ability to initiate photo-radical polymerization, it is also preferred that the composition of the present invention contains the above-mentioned organometallic complex and a radical polymerization initiator. According to this aspect, the generation of development residues, line breaks of patterns, etc. as described above can be suppressed, and the exposure sensitivity is also improved. When the composition of the present invention contains an organic metal complex that does not have the ability to start photoradical polymerization, it is preferred that the composition of the present invention contains a photoradical polymerization initiator. It is believed that since the composition of the present invention contains a specific resin, the aggregation of the organic metal complex can be suppressed. It is believed that by suppressing the aggregation of the organic metal complex that does not have the ability to start photoradical polymerization, the increase in the plasticity of the local film caused by aggregation can be suppressed, and the increase in the local polymerization degree in the aggregation site can also be suppressed. As a result, it is believed that the generation of sensitivity deviation caused by the site of the film can be suppressed, and the resolution is improved. When the composition of the present invention includes an organic metal complex and a photo-radical polymerization initiator, the content of the organic metal complex relative to the total content of the organic metal complex and the photo-radical polymerization initiator is preferably 20 to 80 mass %, and more preferably 30 to 70 mass %. In addition, as the above-mentioned photo-radical polymerization initiator, the oxime compound described later is preferred.

The photo-free radical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L•mol ^-1 •cm ^-1 in the range of about 300 to 800 nm (preferably 330 to 500 nm). The molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured by a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.

As the photoradical polymerization initiator, any known compound can be used. For example, alkyl halides derivatives (e.g., compounds having a trioxane skeleton, compounds having a diazole structure, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketone oxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, organic boron compounds, etc. can be cited. For the details thereof, reference can be made to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219, the contents of which are incorporated into this specification.

Examples of the ketone compound include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. Among commercially available products, KAYACURE DETX (manufactured by Nippon Kayaku Co., Ltd.) can also be preferably used.

In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds and acylphosphine compounds can be preferably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in Japanese Patent Publication No. 10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used.

As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone-based initiator, commercially available products such as IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF Corporation) can be used.

As the aminoacetophenone-based initiator, the compound described in Japanese Patent Application Publication No. 2009-191179, which has an absorption maximum wavelength matching a light source of wavelength such as 365 nm or 405 nm, can also be used.

Examples of the acylphosphine-based initiator include 2,4,6-trimethylbenzyl-diphenyl-phosphine oxide, etc. Commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.

As a photo-radical polymerization initiator, an oxime compound can be more preferably cited. By using an oxime compound, the exposure latitude can be more effectively improved. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photohardening accelerator.

Specific examples of the oxime compound include compounds described in Japanese Patent Application Laid-Open No. 2001-233842, compounds described in Japanese Patent Application Laid-Open No. 2000-080068, and compounds described in Japanese Patent Application Laid-Open No. 2006-342166.

Preferred oxime compounds include, for example, compounds having the following structures or 3-benzyloxyiminobutane-2-one, 3-acetyloxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetyloxyiminopentane-3-one, 2-acetyloxyimino-1-phenylpropane-1-one, 2-benzyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. In the composition of the present invention, it is particularly preferred to use an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator. Oxime-based photopolymerization initiators have a linking group of >C=N-O-C(=O)- in the molecule.

[Chemical formula 29]

Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052) can also be preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-831 and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can also be used. In addition, DFI-091 (manufactured by Daito Chemix Corporation) can be used. In addition, an oxime compound having the following structure can also be used. [Chemical Formula 30]

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compounds described in Japanese Patent Application Publication No. 2014-137466 and the compounds described in Japanese Patent No. 6636081.

As the photopolymerization initiator, an oxime compound having a carbazole ring and at least one benzene ring being a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

In addition, oxime compounds having fluorine atoms can also be used. Specific examples of such oxime compounds include compounds described in Japanese Unexamined Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in paragraph 0345 of Japanese Unexamined Patent Publication No. 2014-500852, and compound (C-3) described in paragraph 0101 of Japanese Unexamined Patent Publication No. 2013-164471.

As the most preferable oxime compound, there can be mentioned an oxime compound having a specific substituent as disclosed in Japanese Patent Application Laid-Open No. 2007-269779 or an oxime compound having a thioaryl group as disclosed in Japanese Patent Application Laid-Open No. 2009-191061.

From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyl trioxane compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzyl-iron complexes and salts thereof, halogenated methyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

Further preferred photoradical polymerization initiators are trihalogenomethyl trioxane compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds. At least one compound selected from the group consisting of trihalogenomethyl trioxane compounds, α-amino ketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds is further preferred. Using metallocene compounds or oxime compounds is further preferred, and oxime compounds are still further preferred.

In addition, the photoradical polymerization initiator may include benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone (Michelle's ketone) and the like, aromatic ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propanone-1, quinones with aromatic ring condensation such as alkyl anthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin and benzoin compounds such as alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, and the like. In addition, the compound represented by the following formula (I) may be used.

[Chemical formula 31]

In the formula (I), R ^I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by one or more oxygen atoms, and a phenyl group or a biphenyl group substituted by at least one of an alkyl group having 1 to 4 carbon atoms, R ^I01 is a group represented by the formula (II) or a group identical to R ^I00 , and R ^I02 to R ^I04 are each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.

[Chemical formula 32]

In the formula, R ^I05 to R ^I07 are the same as R ^I02 to R ^I04 in the above formula (I).

Furthermore, the photoradical polymerization initiator may also include the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/125469.

When a photopolymerization initiator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, further preferably 0.5 to 15 mass %, and further preferably 1.0 to 10 mass %. The photopolymerization initiator may contain only one type or two or more types. When two or more photopolymerization initiators are included, their total amount is preferably within the above range.

[Photoacid generator] In addition, in the composition of the present invention, it is also preferable to include a photoacid generator as a photosensitive agent. By including a photoacid generator, for example, acid is generated in the exposed part of the photosensitive film, and the solubility of the exposed part in the developer (for example, alkaline aqueous solution) increases, and a positive pattern in which the exposed part is removed by the developer can be obtained. In addition, it is also possible to set it as follows: by the composition containing a photoacid generator and a crosslinking agent other than the free radical crosslinking agent described later, for example, the crosslinking reaction of the crosslinking agent is promoted by the acid generated in the exposed part, and the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include quinone diazonium compounds, onium salt compounds such as diazo salts, phosphonium salts, coronium salts, and iodonium salts, sulfonate compounds such as acylimide sulfonates, oxime sulfonates, diazo disulfonates, disulfonates, and o-nitrobenzyl sulfonates.

Examples of the quinone diazide compound include a quinone diazide sulfonic acid bonded to a polyhydroxy compound via an ester bond, a quinone diazide sulfonic acid bonded to a polyamine compound via a sulfonamide bond, a quinone diazide sulfonic acid bonded to a polyhydroxy polyamine compound via an ester bond and a sulfonamide bond, etc. In the present invention, for example, preferably, 50 mol% or more of the functional groups of the polyhydroxy compound or polyamine compound are substituted with quinone diazide groups.

In the present invention, the quinone diazide can preferably use either 5-naphthoquinone diazide sulfonyl or 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl compound has absorption in the i-ray region of a mercury lamp and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl compound extends to the g-ray region of a mercury lamp and is suitable for g-ray exposure. In the present invention, the 4-naphthoquinone diazide sulfonyl compound or the 5-naphthoquinone diazide sulfonyl compound is preferably selected according to the exposure wavelength. Furthermore, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or it may contain a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using such naphthoquinone diazide compounds, the resolution, sensitivity, and residual film rate are further improved. As the naphthoquinone diazide compound, for example, 1,2-naphthoquinone-2-diazido-5-sulfonic acid or 1,2-naphthoquinone-2-diazido-4-sulfonic acid, salts or ester compounds of such compounds, etc. can be cited.

Examples of the onium salt compound or the sulfonate salt compound include compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.

The photoacid generator is preferably a compound containing an oxime sulfonate group (hereinafter, also referred to as an "oxime sulfonate compound"). The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but an oxime sulfonate compound represented by the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104) or the formula (OS-105) is preferred.

[Chemical formula 33]

In formula (OS-1), X ³ represents an alkyl group, an alkoxy group or a halogen atom. When there are multiple X ³ , they may be the same or different. The alkyl group and alkoxy group in the above X ³ may have a substituent. As the alkyl group in the above X ^{3, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred. As the alkoxy group in the above X 3} , a linear or branched alkoxy group having 1 to 4 carbon atoms is preferred. As the halogen atom in the above X ³ , a chlorine atom or a fluorine atom is preferred. In formula (OS-1), m3 represents an integer from 0 to 3, preferably 0 or ^1. When m3 is 2 or 3, the multiple X ³ may be the same or different. In formula (OS-1), R ³⁴ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthracenyl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, or a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.

In the formula (OS-1), the compound wherein m3 is 3, ^X3 is methyl, the substitution position of ^X3 is an ortho position, and ^R34 is a linear alkyl group having 1 to 10 carbon atoms, 7,7-dimethyl-2-oxonorthomethyl or p-tolyl is particularly preferred.

Specific examples of the oxime sulfonate compound represented by formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of JP-A-2011-209692 and paragraphs 0158 to 0167 of JP-A-2015-194674, and the contents thereof are incorporated herein.

[Chemical formula 34]

In formula (OS-103) to formula (OS-105), R ^s1 represents an alkyl group, an aryl group or a heteroaryl group, a plurality of R ^s2 may exist and each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, a plurality of R ^s6 may exist and each independently represents a halogen atom, an alkyl group, an alkoxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group, Xs represents O or S, ns represents 1 or 2, and ms represents an integer of 0 to 6. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), aryl group (preferably having 6 to 30 carbon atoms) or heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R ^s1 may have a substituent T.

In formula (OS-103) to formula (OS-105), R ^s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms), and a hydrogen atom or an alkyl group is more preferred. In a compound, when there are two or more R ^s2 , one or two of them are preferably an alkyl group, an aryl group or a halogen atom, one is more preferably an alkyl group, an aryl group or a halogen atom, and one is particularly preferably an alkyl group and the rest are hydrogen atoms. The alkyl group or aryl group represented by ^{R s2} may have a substituent T. In formula (OS-103), formula (OS-104) or formula (OS-105), Xs represents O or S, and O is preferred. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.

In formula (OS-103) to formula (OS-105), ns represents 1 or 2. When Xs is O, ns is preferably 1. When Xs is S, ns is preferably 2. In formula (OS-103) to formula (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by R ^s6 may have a substituent. In formula (OS-103) to formula (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0.

Furthermore, the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the above formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109). [Chemical Formula 35]

In formula (OS-106) to formula (OS-111), R ^t1 represents an alkyl group, an aryl group or a heteroaryl group, R ^t7 represents a hydrogen atom or a bromine atom, R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R ^t2 represents a hydrogen atom or a methyl group. In formula (OS-106) to formula (OS-111), R ^t7 represents a hydrogen atom or a bromine atom, and a hydrogen atom is preferably used.

In formula (OS-106) to formula (OS-111), R ^t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group.

In formula (OS-106) to formula (OS-111), R ^t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom. R ^t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in the above-mentioned oxime sulfonate compound, the stereostructure (E, Z) of the oxime may be any one of them or a mixture. As specific examples of the oxime sulfonate compounds represented by the above-mentioned formula (OS-103) to formula (OS-105), the compounds described in paragraphs 0088 to 0095 of Japanese Patent Application Publication No. 2011-209692 and paragraphs 0168 to 0194 of Japanese Patent Application Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification.

As another preferred embodiment of the oxime sulfonate compound containing at least one oxime sulfonate group, compounds represented by the following formula (OS-101) and formula (OS-102) can be cited.

[Chemical formula 36]

In formula (OS-101) or (OS-102), R ^u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfonyl group, a sulfonyl group, a cyano group, an aryl group, or a heteroaryl group. It is more preferred that R ^u9 is a cyano group or an aryl group, and it is further preferred that R ^u9 is a cyano group, a phenyl group, or a naphthyl group. In formula (OS-101) or (OS-102), R ^u2a represents an alkyl group or an aryl group. In formula (OS-101) or (OS-102), Xu represents -O-, -S-, -NH-, -NR ^u5 -, -CH ₂ -, -CR ^u6 H-, or CR ^u6 R ^u7 -, and R ^u5 to R ^u7 each independently represent an alkyl group or an aryl group.

In formula (OS-101) or formula (OS-102), R ^u1 to R ^u4 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfonic group, a cyano group or an aryl group. Two of R ^u1 to R ^u4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with a benzene ring. As R ^u1 to R ^u4 , a hydrogen atom, a halogen atom or an alkyl group is preferred, and at least two of R ^u1 to R ^u4 are bonded to each other to form an aryl group. Among them, the embodiment in which all of R ^u1 to R ^u4 are hydrogen atoms is preferred. The above substituents may further have substituents.

The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102). In addition, in the above oxime sulfonate compound, the stereostructure (E, Z, etc.) of the oxime or benzothiazole ring may be any one of them, or a mixture. As specific examples of the compound represented by the formula (OS-101), the compounds described in paragraphs 0102 to 0106 of Japanese Patent Publication No. 2011-209692 and paragraphs 0195 to 0207 of Japanese Patent Publication No. 2015-194674 can be exemplified, and the contents are incorporated into this specification. Among the above compounds, the following b-9, b-16, b-31, and b-33 are also preferred. [Chemical Formula 37]

In addition, commercial products may be used as the photoacid generator. Examples of commercial products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), Omnicat 250 and Omnicat 270 (all manufactured by IGM Resins B.V.), Irgacure 250, Irgacure 270, and Irgacure 290 (all manufactured by BASF), and MBZ-101 (manufactured by Midori Kagaku Co., Ltd.).

Furthermore, as a more preferred example, a compound represented by the following structural formula can also be cited. [Chemical Formula 38]

As photoacid generators, organic halogenated compounds can also be used. As organic halogenated compounds, specifically, there can be cited Wakabayashi et al., "Bull Chem. Soc Japan" 42, 2924 (1969), U.S. Patent No. 3,905,815, Japanese Patent Publication No. 46-004605, Japanese Patent Application Publication No. 48-036281, Japanese Patent Application Publication No. 55-032070, Japanese Patent Application Publication No. 60-239736, Japanese Patent Application Publication No. 61-169835, Japanese Patent Application Publication No. 61-169837, Japanese Patent Application Publication No. 62-058241, Japanese Patent Application Publication No. 62-212401, Japanese Patent Application Publication No. 63-070243, Japanese Patent Application Publication No. 63-298339, M.P. Hutt, "Jurnal of Heterocyclic The compounds described in "Chemistry" 1 (No. 3), (1970), etc., in particular, can be cited as trihalomethyl-substituted oxadiazole compounds: S-triazole compounds. More preferably, s-triazole derivatives in which at least one mono-, di- or trihalomethyl-substituted methyl group is bonded to the s-triazole ring can be cited. Specifically, for example, 2,4,6-tris(monochloromethyl)-s-triazole, 2,4,6-tris(dichloromethyl)-s-triazole, 2,4,6-tris(trichloromethyl)-s-triazole, 2-methyl-4,6-bis(trichloromethyl)-s-triazole, 2-n-propyl-4,6-bis(trichloromethyl)-s-triazole can be cited. tris-1-nitropropene, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-tris-1-nitropropene, phenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-isopropoxyphenyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-trisinyl, 2-(4-naphthyl)- s-triazine, 2-naphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6-bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, etc.

As the photoacid generator, an organic borate compound can also be used. As the organic borate compound, specific examples thereof include Japanese Patent Publication No. 62-143044, Japanese Patent Publication No. 62-150242, Japanese Patent Publication No. 9-188685, Japanese Patent Publication No. 9-188686, Japanese Patent Publication No. 9-188710, Japanese Patent Publication No. 2000-131837, Japanese Patent Publication No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, and Kunz, Martin "Rad Tech '98. Proceeding April 19-22, 1998, Chicago" etc., the organic borate salts described in Japanese Patent Publication No. 6-157623, Japanese Patent Publication No. 6-175564, Japanese Patent Publication No. 6-175561, the organic boron-zirconium complexes or organic boron-oxygen-zirconium complexes described in Japanese Patent Publication No. 6-175554, Japanese Patent Publication No. 6-175553 The organic boron phosphonium complexes described in Japanese Patent Application Publication No. 9-188710, the organic boron transition metal coordination complexes described in Japanese Patent Application Publication No. 6-348011, Japanese Patent Application Publication No. 7-128785, Japanese Patent Application Publication No. 7-140589, Japanese Patent Application Publication No. 7-306527, Japanese Patent Application Publication No. 7-292014, etc.

As the photoacid generator, a disulfide compound can also be used. Examples of the disulfide compound include compounds described in Japanese Patent Application Laid-Open No. 61-166544, Japanese Patent Application No. 2001-132318, and diazodisulfide compounds.

Examples of the onium salt compounds include S.I.Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T.S.Bal et al. al, Polymer, 21,423 (1980), the diazonium salts described in U.S. Patent No. 4,069,055, Japanese Patent Laid-Open No. 4-365049, etc., the phosphonium salts described in the specifications of U.S. Patent No. 4,069,055 and U.S. Patent No. 4,069,056, the specifications of European Patent No. 104,143, U.S. Patent No. 339,049, U.S. Patent No. 410,201, the iodine salts described in Japanese Patent Laid-Open No. 2-150848 and Japanese Patent Laid-Open No. 2-296514, European Patent No. 370,693, European Patent No. 390, 214, European Patent No. 233,567, European Patent No. 297,443, European Patent No. 297,442, U.S. Patent No. 4,933,377, U.S. Patent No. 161,811, U.S. Patent No. 410,201, U.S. Patent No. 339,049, U.S. Patent No. 4,760,013, U.S. Patent No. 4,734,444, U.S. Patent No. 2,833,827, German Patent No. 2,904,626, German Patent No. 3,604,580, German Patent No. 3,604,581, J.V.Crivello et al, Macromolecules, 10 (6), 1307 (1977), selenium salts described in J.V.Crivello et al, J.Polymer Sci., Polymer Chem.Ed., 17, 1047 (1979), arsenic salts, pyridinium salts and other onium salts described in C.S.Wen et al, Teh, Proc.Conf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), etc.

Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III). [Chemical Formula 39] In formula (RI-I), Ar ₁₁ represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z11- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In terms of stability, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, and sulfinic acid ions are preferred. In formula (RI-II), Ar ₂₁ and Ar ₂₂ each independently represent an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z ₂₁ ^- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfuric acid ion. In terms of stability and reactivity, perchlorate ions, hexafluorophosphate ions, tetrafluoroborate ions, sulfonic acid ions, sulfinic acid ions, or carboxylic acid ions are preferred. In formula (RI-III), R ₃₁ , R ₃₂ , and R ₃₃ each independently represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms and which may have 1 to 6 substituents. In terms of reactivity and stability, an aryl group is preferred. Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamide group or an arylamide group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. ^Z31- represents a monovalent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, a thiosulfonic acid ion, or a sulfate ion. In terms of stability and reactivity, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonic acid ion, a sulfinic acid ion, or a carboxylic acid ion is preferred.

As a specific example, the following can be cited. [Chemical formula 40] [Chemical formula 41] [Chemical formula 42] [Chemical formula 43]

When a photoacid generator is included, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass %. The photoacid generator may contain only one type or two or more types. When two or more types of photoacid generators are included, their total content is preferably within the above range.

[Photobase generator] The curable resin composition of the present invention may contain a photobase generator as a photosensitizer. By containing a photobase generator and a crosslinking agent described below in the curable resin composition, for example, the alkali generated in the exposed part promotes the cyclization of a specific resin, promotes the crosslinking reaction of the crosslinking agent, etc., so that the exposed part is less likely to be removed by the developer than the non-exposed part. According to this aspect, a negative pattern can be obtained.

The photoalkali generator is not particularly limited as long as it generates alkali by exposure, and any known one can be used. For example, M. Shirai and M. Tsunooka, Prog. Polym. Sci., 21, 1 (1996); Masahiro Kadoka, Polymer Processing, 46, 2 (1997); C. Kutal, Coord. Chem. Rev., 211, 353 (2001); Y. Kaneko, A. Sarker, and D. Neckers, Chem. Mater., 11, 170 (1999); H. Tachi, M. Shirai, and M. Tsunooka, J. Photopolym. Sci. Technol., 13, 153 (2000); M. Winkle, and K. Graziano, J. Photopolym. Sci. Technol., 3, 419 (1990); M. Tsunooka, H. Tachi, and S.Yoshitaka, J.Photopolym.Sci.Technol., 9, 13 (1996); K.Suyama, H.Araki, M.Shirai, J.Photopolym.Sci.Technol., 19, 81 (2006) state that transition metal compound complexes, substances having structures such as ammonium salts, substances whose amidine moieties are oxidized by forming salts with carboxylic acids, ionic compounds whose base components are neutralized by forming salts, and non-ionic compounds whose base components are oxidized by carbamate bonds or oxime bonds, such as carbamate derivatives, oxime ester derivatives, and acyl compounds. In the present invention, more preferred examples of the photoalkali generator include carbamate derivatives, amide derivatives, imide derivatives, α-cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, and the like.

The alkaline substance generated from the photoalkali generator is not particularly limited, and compounds having an amino group, especially polyamines such as monoamines and diamines, and amidines can be cited. From the perspective of the imidization rate, the alkaline substance preferably has a larger pKa in DMSO (dimethyl sulfoxide) of the conjugated acid. The pKa is preferably 1 or more, and 3 or more is more preferred. There is no particular upper limit for the pKa, and 20 or less is preferred. Here, the pKa represents the logarithm of the reciprocal of the first dissociation constant of an acid, and can be found in Determination of Organic Structures by Physical Methods (author: Brown, H. C., McDaniel, D. H., Hafliger, O., Nachod, F. C.; editor: Braude, E. A., Nachod, F. C.; Academic Press, New York, 1955) or Data for Biochemical Research (author: Dawson, R.M.C. et al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, the value calculated from the structural formula was used as pKa using software ACD/pKa (manufactured by ACD/Labs).

From the perspective of storage stability of the curable resin composition, it is preferable that the photoalkali generator does not contain salt in its structure, and it is preferable that the nitrogen atom of the alkali portion generated in the photoalkali generator has no charge. It is preferable that the generated alkali is potentially converted by covalent bonds, and it is preferable that the alkali generation mechanism is a mechanism in which the covalent bonds between the nitrogen atom of the generated alkali portion and the adjacent atom are cut to generate the alkali. If the photoalkali generator does not contain salt in its structure, the photoalkali generator can be made neutral, so that the solvent solubility is better and the shelf life is extended. For these reasons, the amine generated by the photobase generator used in the present invention is preferably a primary amine or a secondary amine. In addition, from the viewpoint of the chemical resistance of the pattern, as a photobase generator, a photobase generator containing a salt in its structure is preferred.

Furthermore, considering the above reasons, as a photoalkali generator, as mentioned above, the generated base is preferably potentially transformed using a covalent bond, and the generated base is preferably potentially transformed using an amide bond, a carbamate bond, or an oxime bond. As the photobase generator of the present invention, for example, a photobase generator having a cinnamylamide structure as disclosed in Japanese Patent Application Publication No. 2009-080452 and International Publication No. 2009/123122, a photobase generator having a carbamate structure as disclosed in Japanese Patent Application Publication No. 2006-189591 and Japanese Patent Application Publication No. 2008-247747, a photobase generator having an oxime structure or an aminoformyl oxime structure as disclosed in Japanese Patent Application Publication No. 2007-249013 and Japanese Patent Application Publication No. 2008-003581, etc. can be cited, but the present invention is not limited to these, and other known photobase generator structures can be used.

In addition, as examples of photoalkali generators, compounds described in paragraphs 0185 to 0188, 0199 to 0200, and 0202 of Japanese Patent Application Laid-Open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese Patent Application Laid-Open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese Patent Application Laid-Open No. 2013-204019, and compounds described in paragraph 0052 of International Publication No. 2010/064631 can be cited.

As the photoalkali generator, a commercial product may be used. Examples of the commercial product include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, WPBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), and A2502, B5085, N0528, N1052, O0396, O0447, and O0448 (manufactured by Tokyo Chemical Industry Co., Ltd.).

When a photobase generator is included, its content is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and even more preferably 2 to 15 mass % relative to the total solid content of the curable resin composition of the present invention. The photobase generator may contain only one type or two or more types. When two or more types of photobase generators are contained, the total amount thereof is preferably within the above range.

<Thermal polymerization initiator> The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal free radical polymerization initiator. A thermal free radical polymerization initiator is a compound that generates free radicals by heat energy to initiate or promote the polymerization reaction of a polymerizable compound. By adding a thermal free radical polymerization initiator, the polymerization reaction of the resin and the crosslinking agent also proceeds in the heating process described later, thereby further improving the solvent resistance.

Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.

When a thermal polymerization initiator is contained, its content relative to the total solid content of the composition of the present invention is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, and further preferably 0.5 to 15 mass %. The thermal polymerization initiator may contain only one kind or two or more kinds. When two or more thermal polymerization initiators are contained, their total amount is preferably within the above range.

<Thermal acid generator> The composition of the present invention may contain a thermal acid generator. The thermal acid generator has the following effect: by generating an acid by heating, the cross-linking reaction of at least one compound selected from compounds having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxycyclobutane compound and a benzophenone compound is promoted.

The thermal decomposition start temperature of the thermal acid generator is preferably 50℃ to 270℃, and more preferably 50℃ to 250℃. In addition, if a thermal acid generator is selected that does not generate acid during drying (pre-baking: about 70 to 140℃) after the composition is applied to the substrate, but generates acid during the final heating (hardening: about 100 to 400℃) after patterning in the subsequent exposure and development, it is preferred because the sensitivity drop during development can be suppressed. The thermal decomposition start temperature is obtained as the peak temperature of the lowest temperature heat peak when the thermal acid generator is heated to 500℃ at 5℃/min in a pressure-resistant capsule. As an instrument used to measure the thermal decomposition starting temperature, Q2000 (manufactured by TA Instruments) and the like can be cited.

The acid generated from the thermal acid generator is preferably a strong acid, for example, an arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, an alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, or a halogenated alkylsulfonic acid such as trifluoromethanesulfonic acid. Examples of such thermal acid generators include those described in paragraph 0055 of Japanese Patent Application Publication No. 2013-072935.

Among them, from the viewpoint of less residue in the organic film and less deterioration of the physical properties of the organic film, those that produce alkylsulfonic acids having 1 to 4 carbon atoms or halogenated alkylsulfonic acids having 1 to 4 carbon atoms are more preferred, such as (4-hydroxyphenyl)dimethylcoppersulfonate, (4-((methoxycarbonyl)oxy)phenyl)dimethylcoppersulfonate, benzyl(4-hydroxyphenyl)methylcoppersulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcoppersulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)coppersulfonate, (4-hydroxyphenyl)dimethylcoppersulfonate, Preferred as the thermal acid generator are (4-((methoxycarbonyl)oxy)phenyl)dimethylcopperium trifluoromethanesulfonate, benzyl(4-hydroxyphenyl)methylcopperium trifluoromethanesulfonate, benzyl(4-((methoxycarbonyl)oxy)phenyl)methylcopperium trifluoromethanesulfonate, (4-hydroxyphenyl)methyl((2-methylphenyl)methyl)copperium trifluoromethanesulfonate, 3-(5-(((propylsulfonyl)oxy)imino)thiophen-2(5H)-ylidene)-2-(o-tolyl)propionitrile, and 2,2-bis(3-(methanesulfonylamino)-4-hydroxyphenyl)hexafluoropropane.

Furthermore, the compound described in paragraph 0059 of JP-A-2013-167742 is also preferred as a thermal acid generator.

The content of the thermal acid generator is preferably 0.01 parts by mass or more, and more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. By containing 0.01 parts by mass or more, the crosslinking reaction is promoted, thereby further improving the mechanical properties and solvent resistance of the organic film. In addition, from the viewpoint of the electrical insulation of the organic film, 20 parts by mass or less is preferably, 15 parts by mass or less is more preferably, and 10 parts by mass or less is even more preferably.

<Onium salt> The curable resin composition of the present invention may further contain an onium salt. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt. The type of onium salt is not particularly specified, and ammonium salts, ammonium salts, stibnium salts, iodine salts or phosphonium salts can be preferably cited. Among them, ammonium salts or ammonium salts are preferred from the viewpoint of high thermal stability, and cobalt salts, iodonium salts or phosphonium salts are preferred from the viewpoint of compatibility with polymers.

Furthermore, an onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may be bonded by covalent bonding or not. That is, the onium salt may be an intramolecular salt having a cation part and anion part in the same molecular structure, or an intermolecular salt formed by ionic bonding of cation molecules and anion molecules of different molecules, but an intermolecular salt is preferred. Furthermore, in the curable resin composition of the present invention, the cation part or cation molecule and the anion part or anion molecule may be bonded by ionic bonding or may be dissociated. As the cation in the onium salt, an ammonium cation, a pyridinium cation, a coronium cation, an iodine cation or a phosphonium cation is preferred, and at least one cation selected from the group consisting of tetraalkylammonium cations, coronium cations and iodine cations is more preferred.

The onium salt used in the present invention may be a thermal alkali generator described below. The thermal alkali generator refers to a compound that generates a base by heating, and examples thereof include compounds that generate a base when heated to 40°C or higher. As the onium salt, for example, onium salts described in paragraphs 0122 to 0138 of International Publication No. 2018/043262 may be cited. In addition, onium salts used in the field of polyimide precursors may be used without particular limitation.

When the curable resin composition of the present invention contains an onium salt, the content of the onium salt relative to the total solid content of the curable resin composition of the present invention is preferably 0.1 to 50 mass %. The lower limit is preferably 0.5 mass %, more preferably 0.85 mass %, and more preferably 1 mass %. The upper limit is preferably 30 mass %, more preferably 20 mass %, and more preferably 10 mass %, and can also be 5 mass %, and can also be 4 mass %. The onium salt can be used alone or in combination. When two or more are used, the total amount is preferably within the above range.

<Thermal alkali generator> The curable resin composition of the present invention may further contain a thermal alkali generator. In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal alkali generator. Other thermal alkali generators may be compounds corresponding to the above-mentioned onium salts, or thermal alkali generators other than the above-mentioned onium salts. As thermal alkali generators other than the above-mentioned onium salts, non-ionic thermal alkali generators can be cited. As non-ionic thermal alkali generators, compounds represented by formula (B1) or formula (B2) can be cited. [Chemical formula 44]

In formula (B1) and formula (B2), ^Rb1 , ^Rb2 and ^Rb3 are independently an organic group, a halogen atom or a hydrogen atom that does not have a tertiary amine structure. However, ^Rb1 and ^Rb2 will not be hydrogen atoms at the same time. Moreover, ^Rb1 , ^Rb2 and ^Rb3 will not all have carboxyl groups. In addition, in this specification, a tertiary amine structure refers to a structure in which the three bonds of a trivalent nitrogen atom are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, when the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, when it forms an amide group together with a nitrogen atom, it is not limited to this.

In formula (B1) and (B2), at least one of ^Rb1 , ^Rb2 and ^Rb3 preferably has a cyclic structure, and at least two of them more preferably have a cyclic structure. The cyclic structure may be a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring formed by condensing two monocyclic rings is preferred. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, and a 6-membered ring is preferred. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and a cyclohexane ring is more preferred.

More specifically, ^Rb1 and ^Rb2 are preferably hydrogen atoms, alkyl groups (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), alkenyl groups (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 10 carbon atoms), or arylalkyl groups (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms). These groups may have substituents within the scope of exerting the effects of the present invention. ^Rb1 and ^Rb2 may be bonded to each other to form a ring. As the formed ring, a 4-7-membered nitrogen-containing heterocyclic ring is preferred. ^Rb1 and ^Rb2 are particularly preferably linear, branched or cyclic alkyl groups which may have a substituent (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), more preferably cycloalkyl groups which may have a substituent (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and further preferably 3 to 12 carbon atoms), and further preferably cyclohexyl groups which may have a substituent.

Examples of Rb ³ include alkyl (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryl (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), alkenyl (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 6 carbon atoms), arylalkyl (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), Arylalkenyl (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, and more preferably 8 to 16 carbon atoms), alkoxy (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), aryloxy (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or arylalkoxy (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms). Among them, cycloalkyl (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), arylalkenyl, and arylalkoxy are preferred. ^Rb3 may further have a substituent within the range in which the effect of the present invention is exerted.

The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2). [Chemical Formula 45]

In the formula, ^Rb11 and ^Rb12 as well as ^Rb31 and ^Rb32 are the same as ^Rb1 and ^Rb2 in formula (B1), respectively. ^Rb13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 12 carbon atoms), and may have a substituent within the range in which the effect of the present invention is exerted. Among them, ^Rb13 is preferably an arylalkyl group.

^Rb33 and ^Rb34 are independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably a hydrogen atom.

Rb ³⁵ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), and aryl group is preferred.

The compound represented by formula (B1-1) is also preferably a compound represented by formula (B1-1a). [Chemical Formula 46]

^Rb11 and ^Rb12 have the same meanings as ^Rb11 and ^Rb12 in formula (B1-1). ^Rb15 and ^Rb16 are hydrogen atoms, alkyl groups (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms), alkenyl groups (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 3 carbon atoms), aryl groups (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms), arylalkyl groups (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and more preferably 7 to 11 carbon atoms), preferably hydrogen atoms or methyl groups. Rb ¹⁷ is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and further preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and further preferably 6 to 12 carbon atoms), or an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and further preferably 7 to 12 carbon atoms), wherein the aryl group is preferred.

The molecular weight of the non-ionic thermal alkali generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. As the lower limit, it is preferably 100 or more, more preferably 200 or more, and further preferably 300 or more.

As specific examples of the compound serving as a thermal alkali generator among the above-mentioned onium salts or specific examples of the thermal alkali generator other than the above-mentioned onium salts, the following compounds can be cited.

[Chemical formula 47]

[Chemical formula 48]

[Chemical formula 49]

The content of other alkali generators is preferably 0.1 to 50% by mass relative to the total solid content of the hardening resin composition of the present invention. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The alkali generator can be used alone or in combination. When two or more types are used, the total amount is preferably within the above range.

<Crosslinking agent> The hardening resin composition of the present invention preferably contains a crosslinking agent. As the crosslinking agent, free radical crosslinking agents or other crosslinking agents can be cited.

<Free radical crosslinking agent> The curable resin composition of the present invention preferably further contains a free radical crosslinking agent. The free radical crosslinking agent is a compound having a free radical polymerizable group. As the free radical polymerizable group, a group containing an ethylenic unsaturated bond is preferred. As the above-mentioned group containing an ethylenic unsaturated bond, there can be cited groups having an ethylenic unsaturated bond such as vinyl, allyl, vinylphenyl, (meth)acryloyl, etc. Among them, as the above-mentioned group containing an ethylenic unsaturated bond, a (meth)acryloyl group is preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.

The free radical crosslinking agent can be any compound having one or more ethylenic unsaturated bonds, and a compound having two or more ethylenic unsaturated bonds is more preferred. The compound having two ethylenic unsaturated bonds is preferably a compound having two of the above-mentioned groups containing ethylenic unsaturated bonds. In addition, from the viewpoint of the film strength of the obtained pattern, it is preferred that the curable resin composition of the present invention contains a compound having three or more ethylenic unsaturated bonds as a free radical crosslinking agent. As the above-mentioned compound having three or more ethylenic unsaturated bonds, a compound having 3 to 15 ethylenic unsaturated bonds is more preferred, a compound having 3 to 10 ethylenic unsaturated bonds is more preferred, and a compound having 3 to 6 ethylenic unsaturated bonds is further preferred. Furthermore, the compound having more than 3 ethylenic unsaturated bonds is preferably a compound having more than 3 groups containing ethylenic unsaturated bonds, a compound having 3 to 15 groups is more preferably, a compound having 3 to 10 groups is further preferably, and a compound having 3 to 6 groups is particularly preferably. Furthermore, from the viewpoint of the film strength of the obtained pattern, the curable resin composition of the present invention preferably contains a compound having 2 ethylenic unsaturated bonds and a compound having 3 or more ethylenic unsaturated bonds.

The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

Specific examples of free radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters and amides, preferably esters of unsaturated carboxylic acids and polyol compounds and amides of unsaturated carboxylic acids and polyamine compounds. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, sulfhydryl groups, etc., and monofunctional or polyfunctional isocyanates or epoxides, or dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids can also be preferably used. Furthermore, addition reaction products of unsaturated carboxylates or amides having electron-withdrawing substituents such as isocyanate groups or epoxy groups and monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylates or amides having dissociative substituents such as halogeno groups or tosyloxy groups and monofunctional or polyfunctional alcohols, amines, and thiols can also be preferably used. Moreover, as another example, a compound group replaced with unsaturated phosphonic acid, vinylbenzene derivatives such as styrene, vinyl ether, allyl ether, etc. can also be used instead of the above unsaturated carboxylic acid. As a specific example, reference can be made to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated into this specification.

In addition, the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di(meth)acrylate, trihydroxymethylethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol (meth)acrylate, trihydroxymethylpropane tri(acryloxypropyl) ether, tri(acryloxyethyl) isocyanurate, glycerol or trihydroxymethylethane, and then (meth)acrylic acid. Esterified compounds, such as urethane (meth) acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 50-006034, Japanese Patent Publication No. 51-037193, polyester acrylates described in Japanese Patent Publication No. 48-064183, Japanese Patent Publication No. 49-043191, Japanese Patent Publication No. 52-030490, epoxy acrylates as reaction products of epoxy resin and (meth) acrylic acid, and mixtures thereof. In addition, compounds described in paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970 are also preferred. In addition, there can be mentioned polyfunctional (meth)acrylates obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth)acrylate with a polyfunctional carboxylic acid.

Furthermore, as a preferred radical crosslinking agent other than the above, a compound having a fluorene ring and having two or more groups containing ethylenic unsaturated bonds, or a cardo resin described in Japanese Patent Application Laid-Open No. 2010-160418, Japanese Patent Application Laid-Open No. 2010-129825, Japanese Patent Application No. 4364216, etc. can also be used.

As other examples, specific unsaturated compounds described in Japanese Patent Publication No. 46-043946, Japanese Patent Publication No. 01-040337, Japanese Patent Publication No. 01-040336, or vinylphosphonic acid compounds described in Japanese Patent Publication No. 02-025493 can be cited. In addition, compounds containing perfluoroalkyl groups described in Japanese Patent Publication No. 61-022048 can also be used. In addition, those introduced as photopolymerizable monomers and oligomers in the Journal of the Japan Association of Adhesion, vol. 20, No. 7, pp. 300-308 (1984) can also be used.

In addition to the above, the compounds described in paragraphs 0048 to 0051 of JP-A-2015-034964 and the compounds described in paragraphs 0087 to 0131 of WO-2015/199219 can also be preferably used, and the contents thereof are incorporated into the present specification.

In addition, compounds described in Japanese Patent Application Laid-Open No. 10-062986 as formula (1) and formula (2) together with specific examples thereof, in which ethylene oxide or propylene oxide is added to a polyfunctional alcohol and then (meth)acrylic acid is esterified, can also be used as a radical crosslinking agent.

In addition, the compounds described in paragraphs 0104 to 0131 of JP-A-2015-187211 can also be used as a radical crosslinking agent, and these contents are incorporated into this specification.

As the free radical crosslinking agent, dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd., A-TMMT: manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.) and the structure in which the (meth)acryloyl group is bonded via an ethylene glycol residue or a propylene glycol residue is preferred. The oligomer type of the same can also be used.

As commercially available free radical crosslinking agents, for example, SR-494 manufactured by Sartomer Company, Inc., which is a tetrafunctional acrylate having four ethoxy chains, SR-209, 231, 239 manufactured by Sartomer Company, Inc., which are bifunctional methacrylates having four ethoxy chains, DPCA-60 manufactured by Nippon Kayaku Co., Ltd., which is a hexafunctional acrylate having six pentyloxy chains, TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains, urethane oligomers UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), BLEMMER PME400 (manufactured by NOF CORPORATION), etc.

As free radical crosslinking agents, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, and urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, as the radical crosslinking agent, compounds having an amino structure or a sulfide structure in the molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-Open No. 01-105238 can also be used.

The free radical crosslinking agent may also be a free radical crosslinking agent having an acid group such as a carboxyl group or a phosphoric acid group. The free radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferably. It is particularly preferred that, in the free radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, the aliphatic polyhydroxy compound is a compound of neopentyl triol or dipentyl triol. As commercially available products, for example, polyacid-modified acrylic oligomers manufactured by TOAGOSEI CO., LTD. include M-510 and M-520.

The preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. If the acid value of the free radical crosslinking agent is within the above range, the operability in production is excellent, and further, the developing property is excellent. In addition, the polymerizability is good. On the other hand, from the viewpoint of the developing speed during alkaline development, the preferred acid value of the free radical crosslinking agent having an acid group is 0.1 to 300 mgKOH/g, and particularly preferably 1 to 100 mgKOH/g. The above acid value is measured in accordance with the description of JIS K 0070:1992.

From the viewpoint of pattern resolution and film stretchability, the curable resin composition of the present invention preferably uses a bifunctional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hex ... Dimethacrylate, dihydroxymethyl-tricyclodecane diacrylate, dihydroxymethyl-tricyclodecane dimethacrylate, bisphenol A EO adduct diacrylate, bisphenol A EO adduct dimethacrylate, bisphenol A PO adduct diacrylate, bisphenol A PO adduct dimethacrylate, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid EO modified diacrylate, isocyanuric acid modified dimethacrylate, and bifunctional acrylate with carbamate bond, bifunctional methacrylate with carbamate bond. Two or more of these can be used in combination as needed. In addition, for example, PEG200 diacrylate refers to polyethylene glycol diacrylate and the formula weight of the polyethylene glycol chain is about 200. Furthermore, from the viewpoint of suppressing warping accompanying the control of the elastic modulus of the pattern, a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional free radical crosslinking agent, (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-hydroxymethyl (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl compounds such as allyl glycidyl ether, diallyl phthalate, and triallyl trimellitate can be preferably used. As a monofunctional free radical crosslinking agent, a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatility before exposure.

When a free radical crosslinking agent is contained, its content is preferably more than 0 mass % and less than 60 mass % relative to the total solid content of the hardening resin composition of the present invention. The lower limit is more preferably 5 mass % or more. The upper limit is more preferably 50 mass % or less, and even more preferably 30 mass % or less.

The free radical crosslinking agent may be used alone or in combination of two or more. When two or more are used in combination, it is preferred that the total amount thereof be within the above range.

<Other crosslinking agents> The curable resin composition of the present invention preferably contains other crosslinking agents different from the above-mentioned free radical crosslinking agents. In the present invention, other crosslinking agents refer to crosslinking agents other than the above-mentioned free radical crosslinking agents, preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the photosensitization of the above-mentioned photosensitive agent, and preferably compounds having multiple groups in the molecule that promote the reaction of forming covalent bonds with other compounds in the composition or their reaction products by the action of acids or bases. The above-mentioned acid or base is preferably an acid or base generated from a photoacid generator or a photoalkali generator as a photosensitive agent in the exposure process. As other crosslinking agents, compounds having at least one group selected from the group including hydroxymethyl and alkoxymethyl are preferred, and compounds having a structure in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to a nitrogen atom are more preferred. As other crosslinking agents, for example, compounds having a structure in which formaldehyde or formaldehyde and alcohol react with compounds containing amino groups such as melamine, glycoluril, urea, alkyl urea, benzoguanamine, etc. to replace the hydrogen atom of the above amino group with hydroxymethyl or alkoxymethyl can be cited. The method for preparing these compounds is not particularly limited, as long as they are compounds having the same structure as the compounds prepared by the above method. In addition, they can also be oligomers formed by self-condensation of hydroxymethyl groups of these compounds. A crosslinking agent using melamine as the above-mentioned amino group-containing compound is called a melamine-based crosslinking agent, a crosslinking agent using glycoluril, urea or alkylene urea is called a urea-based crosslinking agent, a crosslinking agent using alkylene urea is called an alkylene urea-based crosslinking agent, and a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent. Among them, the curable resin composition of the present invention preferably contains at least one compound selected from the group including urea-based crosslinking agents and melamine-based crosslinking agents, and more preferably contains at least one compound selected from the group including glycoluril-based crosslinking agents and melamine-based crosslinking agents described later.

Specific examples of the melamine-based crosslinking agent include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.

Specific examples of urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monoprop ... methylated glycoluril, dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril or tetrabutoxymethylated glycoluril, dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, dibutoxymethyl urea and other urea crosslinking agents, monohydroxymethylated ethyl urea or dihydroxymethyl ethyl urea crosslinking agents such as methylated ethyl urea, monomethoxymethylated ethyl urea, dimethoxymethylated ethyl urea, monoethoxymethylated ethyl urea, diethoxymethylated ethyl urea, monopropoxymethylated ethyl urea, dipropoxymethylated ethyl urea, monobutoxymethylated ethyl urea or dibutoxymethylated ethyl urea, monohydroxymethylated propyl urea, dihydroxymethylated propyl urea, monomethoxymethylated propyl urea, dimethoxymethylated Methylated propylene urea, monoethoxymethylated propylene urea, diethoxymethylated propylene urea, monopropoxymethylated propylene urea, dipropoxymethylated propylene urea, monobutoxymethylated propylene urea or dibutoxymethylated propylene urea and other propylene urea-based crosslinking agents, 1,3-bis(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, etc.

Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.

In addition, as the compound having at least one group selected from the group including hydroxymethyl and alkoxymethyl, a compound in which at least one group selected from the group including hydroxymethyl and alkoxymethyl is directly bonded to an aromatic ring (preferably a benzene ring) can also be preferably used. Specific examples of such compounds include benzyl alcohol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate, bis(hydroxymethyl)biphenyl, dimethylbis(hydroxymethyl)biphenyl, bis(methoxymethyl)benzene, bis(methoxymethyl)cresol, bis(methoxymethyl)dimethoxybenzene, bis(methoxymethyl)diphenyl ether, bis(methoxymethyl) benzophenone, methoxymethylphenyl methoxymethyl benzoate, bis(methoxymethyl)biphenyl, dimethylbis(methoxymethyl)biphenyl, 4,4',4''-ethylenetri[2,6-bis(methoxymethyl)phenol], 5,5'-[2,2,2-trifluoro-1-(trifluoromethyl)ethylene]bis[2-hydroxy-1,3-benzenedimethanol], 3,3',5,5'-tetrakis(methoxymethyl)-1,1'-biphenyl-4,4'-diol, etc.

As other crosslinking agents, commercial products may be used. Preferred commercial products include 46DMOC, 46DMOEP (all manufactured by ASAHI YUKIZAI CORPORATION), DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM -PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), NIKARAC (registered trademark, hereinafter the same) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (all manufactured by Sanwa Chemical Co., Ltd.), etc.

In addition, the curable resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, cyclohexane compounds and benzophenone compounds as another crosslinking agent.

[Epoxy compounds (compounds having epoxy groups)] As epoxy compounds, compounds having two or more epoxy groups in one molecule are preferred. Epoxy groups undergo crosslinking reaction below 200°C and do not produce dehydration reaction derived from crosslinking, so film shrinkage is not likely to occur. Therefore, containing epoxy compounds is effective for low-temperature curing and warping suppression of curable resin compositions.

The epoxy compound preferably contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warping. The polyethylene oxide group refers to a group having 2 or more repeating units of ethylene oxide, preferably 2 to 15 repeating units.

Examples of epoxy compounds include bisphenol A type epoxy resins; bisphenol F type epoxy resins; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trihydroxymethylpropane triglycidyl ether and other alkylene glycol type epoxy resins or polyol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; epoxy group-containing silicones such as polymethyl (glycidyloxypropyl) siloxane, etc., but are not limited to these. Specifically, we can cite EPICLON (registered trademark) 850-S, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICL ON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-830LVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-8169, EPICLON (registered trademark) N-660, EPICLON (registered trademark) N-665-EXP-S, EPICLON (registered trademark) N-740, Rika Resin (registered trademark) BEO-20E (the above are trade names, manufactured by DIC Corporation), Rika Resin (registered trademark) BEO-60E, Rika Resin (registered trademark) HBE-100, Rika Resin (registered trademark) DME-100, Rika Resin (registered trademark) L-200 (trade name, manufactured by New Japan Chemical Co., Ltd.), EP-4003S, EP-4000S, EP-4088S, EP-3950S (the above are trade names, manufactured by ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (the above are product names, Daicel Corporation), NC-3000, NC-3000-L, NC-3000-H, NC-3000-FH-75M, NC-3100, CER-3000-L, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN-501H, EPPN-501HY, EPPN-502H, EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, CER-1020, EPPN-201, BREN-S, BREN-10S (the above are trade names, manufactured by Nippon Kayaku Co., Ltd.), etc.

[Oxycyclobutane compounds (compounds having an oxycyclobutyl group)] Examples of the oxycyclobutane compounds include compounds having two or more oxycyclobutane rings in one molecule, 3-ethyl-3-hydroxymethyloxycyclobutane, 1,4-bis{[(3-ethyl-3-oxycyclobutyl)methoxy]methyl}benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxycyclobutane, and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxycyclobutyl)methyl]ester. As a specific example, ARON OXETANE series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by TOAGOSEI CO., LTD. can be preferably used, and these can be used alone or in combination of two or more.

[Benzotriazole compounds (compounds having a benzoxazolyl group)] Benzotriazole compounds are preferred because they do not produce degassing during curing due to the cross-linking reaction derived from the ring-opening addition reaction, and further reduce thermal shrinkage to suppress the occurrence of warping.

Preferred examples of benzophenone compounds include B-a type benzophenone, B-m type benzophenone, P-d type benzophenone, F-a type benzophenone (these are trade names, manufactured by SHIKOKU CHEMICALS CORPORATION), benzophenone adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzophenone compounds. These may be used alone or in combination of two or more.

The content of other crosslinking agents is preferably 0.1 to 30 mass %, more preferably 0.1 to 20 mass %, even more preferably 0.5 to 15 mass %, and particularly preferably 1.0 to 10 mass % relative to the total solid content of the hardening resin composition of the present invention. The other crosslinking agents may be contained in one type or in two or more types. When two or more other crosslinking agents are contained, it is preferred that the total amount thereof is within the above range.

<Compounds with sulfonamide structure, compounds with thiourea structure> From the viewpoint of improving the adhesion to the substrate of the obtained pattern, it is preferred that the curable resin composition of the present invention further comprises at least one compound selected from the group consisting of compounds with sulfonamide structure and compounds with thiourea structure.

[Compounds having a sulfonamide structure] The sulfonamide structure is a structure represented by the following formula (S-1). [Chemical Formula 50] In formula (S-1), R represents a hydrogen atom or an organic group, and R may form a ring structure by bonding with other structures, and * independently represents the bonding site with other structures. It is preferred that the above R is the same group as ^R2 in the following formula (S-2). The compound having a sulfonamide structure may be a compound having two or more sulfonamide structures, and a compound having one or more sulfonamide structures is preferred.

The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2). [Chemical Formula 51] In formula (S-2), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent organic group, and two or more of R ¹ , R ² and R ³ may be bonded to each other to form a ring structure. It is preferred that R ¹ , R ² and R ³ each independently represent a monovalent organic group. Examples of R ¹ , R ² and R ³ include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl. Examples of the cycloalkyl group include cycloalkyl groups having 5 to 10 carbon atoms, and cycloalkyl groups having 6 to 10 carbon atoms are more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include 6 to 20 carbon atoms, and 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxadiazole ring, a thiazole ring, a pyrazole ring, an isoxadiazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring.

Among these, the compounds wherein R ¹ is an aryl group and R ² and R ³ are independently a hydrogen atom or an alkyl group are preferred.

Examples of compounds having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthylsulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N,N-dimethylmethanesulfonamide, N,N-dimethylethanesulfonamide, N,N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

[Compounds having a thiourea structure] The thiourea structure is represented by the following formula (T-1). [Chemical formula 52] In formula (T-1), ^R4 and ^R5 each independently represent a hydrogen atom or a monovalent organic group, ^R4 and ^R5 may bond to form a ring, ^R4 may bond to other structures to which * is bonded to form a ring structure, ^R5 may bond to other structures to which * is bonded to form a ring structure, and * each independently represents a bonding site to other structures.

^R4 and ^R5 are preferably independently a hydrogen atom. Examples of ^R4 and ^R5 include a hydrogen atom or an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, or a group in which two or more of these groups are combined. As the above-mentioned alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, a 2-ethylhexyl group, etc. are cited. As the above-mentioned cycloalkyl group, a cycloalkyl group having 5 to 10 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of the alkoxy group include alkoxy groups having 1 to 10 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are more preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentyloxy. Examples of the alkoxysilyl group include alkoxysilyl groups having 1 to 10 carbon atoms, and alkoxysilyl groups having 1 to 4 carbon atoms are more preferred. Examples of the alkoxysilyl group include methoxysilyl, ethoxysilyl, propoxysilyl, and butoxysilyl. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, and aryl groups having 6 to 12 carbon atoms are more preferred. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl. Examples of the heterocyclic group include a group obtained by removing one hydrogen atom from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a thiazole ring, a pyrazole ring, an iso-pyrazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridine ring, a piperidine ring, a piperidine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a trihydropyran ring. The compound having a thiourea structure may be a compound having two or more thiourea structures, but a compound having one thiourea structure is preferred.

The compound having a thiourea structure is preferably a compound represented by the following formula (T-2). [Chemical Formula 53] In formula (T-2), R ⁴ to R ⁷ each independently represent a hydrogen atom or a monovalent organic group, and at least two of R ⁴ to R ⁷ may be bonded to each other to form a ring structure.

In formula (T-2), ^R4 and ^R5 are synonymous with ^R4 and ^R5 in formula (T-1), and preferred embodiments are the same. In formula (T-2), ^R6 and ^R7 are preferably independently monovalent organic groups. In formula (T-2), preferred embodiments of monovalent organic groups in ^R6 and ^R7 are the same as preferred embodiments of monovalent organic groups in ^R4 and ^R5 in formula (T-1).

Examples of compounds having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N'-(2-hydroxyethyl)thiourea, 1-adamantylthiourea, N-benzoylthiourea, N,N'-diphenylthiourea, 1-benzyl-phenylthiourea, 1,3-dibutylthiourea, 1,3-diisopropylthiourea, 1,3-dicyclohexylthiourea, 1-(3-(trimethoxysilyl)propyl)-3-methylthiourea, trimethylthiourea, tetramethylthiourea, N,N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimazole, and 1,3-dimethyl-2-thiohydantoin.

[Content] The total content of the compound having a sulfonamide structure and the compound having a thiourea structure relative to the total mass of the hardening resin composition of the present invention is preferably 0.05 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.2 to 3 mass %. The hardening resin composition of the present invention may contain only one compound selected from the group including compounds having a sulfonamide structure and compounds having a thiourea structure, or may contain two or more. When only one compound is contained, the content of the compound is within the above range, and when two or more compounds are contained, the total amount thereof is preferably within the above range.

<Migration inhibitor> The curable resin composition of the present invention preferably further comprises a migration inhibitor. By comprising a migration inhibitor, it is possible to effectively inhibit metal ions from the metal layer (metal wiring) from migrating into the photosensitive film.

The migration inhibitor is not particularly limited, and examples thereof include compounds having a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, triazole ring, oxadiazole ring, thiazole ring, pyrazole ring, isoxadiazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyrimidine ring, pyridine ring, piperidine ring, piperidine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, trioxadiazole ring), thioureas, compounds having a thiohydrin group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole and benzotriazole, and tetrazole compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.

Alternatively, an ion scavenger that captures anions such as halogen ions may be used.

As other migration inhibitors, the rust inhibitor described in paragraph 0094 of Japanese Patent Application Publication No. 2013-015701, the compound described in paragraphs 0073 to 0076 of Japanese Patent Application Publication No. 2009-283711, the compound described in paragraph 0052 of Japanese Patent Application Publication No. 2011-059656, the compound described in paragraphs 0114, 0116 and 0118 of Japanese Patent Application Publication No. 2012-194520, the compound described in paragraph 0166 of International Publication No. 2015/199219, etc. can be used.

As specific examples of the migration inhibitor, the following compounds can be cited.

[Chemical formula 54]

When the hardening resin composition contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass % relative to the total solid content of the hardening resin composition.

The migration inhibitor may be only one kind or two or more kinds. When there are two or more kinds of migration inhibitors, it is preferred that the total amount thereof is within the above range.

<Polymerization inhibitor> The curable resin composition of the present invention preferably contains a polymerization inhibitor.

As the polymerization inhibitor, for example, hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallol, p-tert-butyl-o-catechol (tert-butyl-o-catechol), 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol) Phenol), N-nitroso-N-phenylhydroxylamine aluminum salt, phenothiocyanate, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5-(N-ethyl)- -N-sulfopropylamino)phenol, N-nitrosophenylhydroxylamine first balsammonium salt, N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, bis(4-hydroxy-3,5-tert-butyl)phenylmethane, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-tris(2,4,6-(1H,3H,5H)-trione, 4-hydroxy-2, 2,6,6-tetramethylpiperidinium 1-oxyl radical, phenathiophene, 1,1-diphenyl-2-pyrrolohydrazide, dibutyldithiocarbamate copper (II), nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N,N'-diphenyl-p-phenylenediamine, 2,4-di-tert-butylphenol, di-tert-butylhydroxytoluene, 1,4-naphthoquinone, etc. In addition, the polymerization inhibitor described in paragraph 0060 of Japanese Patent Application Publication No. 2015-127817 and the compounds described in paragraphs 0031 to 0046 of International Publication No. 2015/125469 can also be used.

Furthermore, the following compounds can be used.

[Chemical formula 55]

When the curable resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is, for example, 0.01 to 20.0 mass %, preferably 0.01 to 5 mass %, more preferably 0.02 to 3 mass %, and even more preferably 0.05 to 2.5 mass %, relative to the total solid content of the curable resin composition of the present invention.

The polymerization inhibitor may be one or more than one. When there are two or more polymerization inhibitors, the total amount thereof is preferably within the above range.

<Metal Adhesion Improver> The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used in electrodes or wiring. Examples of metal adhesion improvers include silane coupling agents, aluminum-based adhesion promoters, titanium-based adhesion promoters, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, and amino compounds.

Examples of silane coupling agents include compounds described in paragraph 0167 of International Publication No. 2015/199219, compounds described in paragraphs 0062 to 0073 of Japanese Patent Application Publication No. 2014-191002, compounds described in paragraphs 0063 to 0071 of International Publication No. 2011/080992, compounds described in paragraphs 0060 to 0061 of Japanese Patent Application Publication No. 2014-191252, compounds described in paragraphs 0045 to 0052 of Japanese Patent Application Publication No. 2014-041264, and compounds described in paragraph 0055 of International Publication No. 2014/097594. Furthermore, as described in paragraphs 0050 to 0058 of Japanese Patent Application Laid-Open No. 2011-128358, it is also preferable to use two or more different silane coupling agents. Furthermore, it is also preferable to use the following compounds as silane coupling agents. In the following formula, Et represents an ethyl group.

[Chemical formula 56] As other silane coupling agents, for example, vinyl trimethoxysilane, vinyl triethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidyloxypropyl methyl dimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl methyl diethoxysilane, 3-glycidyloxypropyl triethoxysilane, p-phenylenediyl trimethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl Acyloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyl trimethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-ureidopropyl trialkoxysilane, 3-butylenepropyl methyldimethoxysilane, 3-butylenepropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, 3-trimethoxysilylpropyl succinic anhydride. These can be used alone or in combination of two or more.

[Aluminum-based bonding aid] As aluminum-based bonding aids, for example, tri(ethyl acetylacetate)aluminum, tri(acetylacetone)aluminum, ethyl acetylacetate aluminum diisopropyl, etc. can be cited.

As the metal adhesion improver, the compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass relative to 100 parts by mass of the specific resin. By setting it to above the above lower limit, the adhesion between the pattern and the metal layer becomes good, and by setting it to below the above upper limit, the heat resistance and mechanical properties of the pattern become good. The metal adhesion improver can be only one kind or two or more kinds. When using two or more kinds, it is better that the total is within the above range.

<Metallic Adhesion Improver> The curable resin composition of the present invention preferably contains a metallic adhesion improver for improving adhesion to metal materials used in electrodes or wiring. As the metallic adhesion improver, compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935 can also be used.

The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the polymer precursor containing the heterocyclic ring. By setting it above the above lower limit, the adhesion between the pattern and the metal layer after the heating process becomes good, and by setting it below the above upper limit, the heat resistance and mechanical properties of the hardened material after the heating process become good. The metal adhesion improver can be only one kind or two or more kinds. When two or more kinds are used, it is better that the total is within the above range.

<Other additives> The curable resin composition of the present invention can be formulated with various additives as needed within the scope of obtaining the effects of the present invention, such as sensitizers, chain transfer agents, surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, anti-agglomeration agents, etc. When such additives are formulated, the total amount thereof is preferably set to be less than 3% by weight of the solid content of the curable resin composition.

[Sensitizer] The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs specific active radiation and becomes an electronically excited state. The sensitizer in the electronically excited state comes into contact with a thermal curing accelerator, a thermal free radical polymerization initiator, a photo-free radical polymerization initiator, etc., and produces electron transfer, energy transfer, heat, etc. Thereby, the thermal curing accelerator, the thermal free radical polymerization initiator, and the photo-free radical polymerization initiator undergo chemical changes and decompose, thereby generating free radicals, acids, or bases. Examples of the sensitizer include michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzylidene)cyclopentane, 2,6-bis(4'-diethylaminobenzylidene)cyclohexanone, 2,6-bis(4'-diethylaminobenzylidene)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminophenylallylidenedihydroindanone, p-Dimethylaminobenzylidenedihydroindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthylthiazole, 1,3-bis(4'-dimethylaminobenzylidene)acetone, 1,3-bis(4'-diethylaminobenzylidene)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethyl 3-Methoxycarbonyl-7-dimethylaminocoumarin, 3-Benzyloxycarbonyl-7-dimethylaminocoumarin, 3-Methoxycarbonyl-7-diethylaminocoumarin, 3-Ethoxycarbonyl-7-diethylaminocoumarin, N-Phenyl-N'-ethylethanolamine, N-Phenyldiethanolamine, N-p-Tolyldiethanolamine, N-Phenylethanolamine, 4-Phenylbenzophenone, Isoamyl dimethylaminobenzoate, Diethylaminobenzyl isopentyl ester, 2-benzimidazole, 1-phenyl-5-benzyltetrazolyl, 2-benzthiazole, 2-(p-dimethylaminostyrene)benzoxazole, 2-(p-dimethylaminostyrene)benzothiazole, 2-(p-dimethylaminostyrene)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc. As the sensitizer, a sensitizing dye can also be used. For details of the sensitizing dye, reference can be made to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which is incorporated into this specification.

When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20 mass %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass % relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.

[Chain transfer agent] The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer Dictionary (edited by the Polymer Society, 2005), pages 683-684. As chain transfer agents, for example, a group of compounds having SH, PH, SiH and GeH in the molecule can be used. These can generate free radicals by supplying hydrogen to low-activity free radicals, or generate free radicals by deprotonation after oxidation. In particular, thiol compounds can be preferably used.

In addition, the chain transfer agent may also include compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be only one type or may be two or more types. When there are two or more types of chain transfer agents, it is preferred that the total amount of the chain transfer agents is within the above range.

[Surfactant] From the viewpoint of further improving the coating properties, a surfactant can be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used. In addition, the following surfactants are also preferred. In the following formula, the parentheses representing the repeating units of the main chain represent the content of each repeating unit (molar %), and the parentheses representing the repeating units of the side chain represent the number of repetitions of each repeating unit. [Chemical Formula 57] In addition, the surfactant may also use compounds described in paragraphs 0159 to 0165 of International Publication No. 2015/199219. As for fluorine-based surfactants, fluorine-containing polymers having ethylenically unsaturated groups in the side chains may also be used as fluorine-based surfactants. As specific examples, compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation, may be cited.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40 mass %, more preferably 5 to 30 mass %, and particularly preferably 7 to 25 mass %. From the perspective of uniformity of the coating thickness or liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective and has good solubility in the composition.

Examples of the silicone-based surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP341, KF6001, and KF6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK307, BYK323, and BYK330 (all manufactured by BYK Chemie GmbH).

Examples of hydrocarbon-based surfactants include PIONIN A-76, New Kalgen FS-3PG, PIONIN B-709, PIONIN B-811-N, PIONIN D-1004, PIONIN D-3104, PIONIN D-3605, PIONIN D-6112, PIONIN D-2104-D, PIONIN D-212, PIONIN D-931, PIONIN D-941, PIONIN D-951, PIONIN E-5310, PIONIN P-1050-B, PIONIN P-1028-P, and PIONIN P-4050-T (all manufactured by Takemoto Oil & Fat Co., Ltd.).

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters, Pluronic (registered trademark) L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Lubrizol Japan Limited.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), Olfine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Specific examples of the cationic surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymer Polyflow No.75, No.77, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

When the curable resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0 mass % relative to the total solid content of the curable resin composition of the present invention, and more preferably 0.005 to 1.0 mass %. The surfactant may be only one kind or two or more kinds. When there are two or more kinds of surfactants, the total amount thereof is preferably within the above range.

[Higher fatty acid derivatives] In order to prevent polymerization hindrance caused by oxygen, the curable resin composition of the present invention may be added with a higher fatty acid derivative such as behenic acid or behenic acid amide so that it is unevenly distributed on the surface of the curable resin composition during the drying process after coating.

Furthermore, the higher fatty acid derivatives may also include the compounds described in paragraph 0155 of International Publication No. 2015/199219.

When the curable resin composition of the present invention contains a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be only one type or may be two or more types. When there are two or more types of higher fatty acid derivatives, their total is preferably within the above range.

[Inorganic particles] The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silicon dioxide, kaolin, talc, titanium dioxide, aluminum oxide, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, etc.

The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. If the average particle size of the inorganic particles is less than 0.01 μm, the mechanical properties of the cured film may deteriorate. If the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.

[Ultraviolet absorber] The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, tris(III)-based ultraviolet absorbers can be used. Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Examples of benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, and 2-hydroxy-4-octyloxybenzophenone. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3'-tert-pentyl-5'-isobutylphenyl)-5-chlorobenzotriazole. 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-[2'-hydroxy-5'-(1,1,3,3-tetramethyl)phenyl]benzotriazole, etc.

Examples of substituted acrylonitrile-based ultraviolet absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate. Examples of tris-based ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-1,2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6 -bis(2,4-dimethylphenyl)-1,3,5-trisinium, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisinium and other mono(hydroxyphenyl)trisinium compounds; 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-trisinium, Bis(hydroxyphenyl)triol compounds such as 2,4-bis(2-hydroxy-3-methyl-4-propoxyphenyl)-6-(4-methylphenyl)-1,3,5-triol, 2,4-bis(2-hydroxy-3-methyl-4-hexyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triol; 2,4-bis(2-hydroxy-4- tris(hydroxyphenyl)tris(iota) compounds such as 2,4-dibutoxyphenyl)-6-(2,4-dibutoxyphenyl)-1,3,5-tris(iota), 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-tris(iota), and 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-tris(iota).

In the present invention, the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more. The composition of the present invention may contain or not contain an ultraviolet absorber, but when containing an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.001 mass % or more and 1 mass % or less, and more preferably 0.01 mass % or more and 0.1 mass % or less relative to the total solid content of the composition of the present invention.

[Organic titanium compound] The resin composition of this embodiment may contain an organic titanium compound. When the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when hardening at a low temperature.

As the organic titanium compounds that can be used, there can be cited those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of the organic titanium compounds are shown in the following I) to VII): I) Titanium chelate compounds: Among them, from the perspective of good storage stability of the negative photosensitive resin composition and the ability to obtain a good cured pattern, titanium chelate compounds having two or more alkoxy groups are more preferred. Specific examples are titanium bis(triethanolamine) diisopropoxide, titanium bis(2,4-pentanedioate) di(n-butoxy), titanium bis(2,4-pentanedioate) diisopropoxy, titanium bis(tetramethylpimelate) diisopropoxy, titanium bis(ethyl acetate) diisopropoxy, etc. II) Tetraalkoxy titanium compounds: for example, tetra(n-butoxy)titanium, tetraethoxytitanium, tetra(2-ethylhexyloxy)titanium, tetraisobutoxytitanium, tetraisopropoxytitanium, tetramethoxytitanium, tetramethylphenoxytitanium, tetra(n-nonoxy)titanium, tetra(n-propoxy)titanium, tetrastearyltitanium, tetra[bis{2,2-(allyloxymethyl)butoxy}]titanium, etc. III) Titanium cyclopentadienyl trimethoxide, for example, titanium pentamethylcyclopentadienyl trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, etc. IV) Titanium monoalkoxy compounds: for example, titanium tris(dioctyl phosphate) isopropoxy, titanium tris(dodecylbenzene sulfonate) isopropoxy, etc. V) Titanium oxide compounds: for example, titanium bis(glutarate) oxide, titanium bis(tetramethylpimelate) oxide, titanium phthalocyanine oxide, etc. VI) Titanium tetraacetylacetonate compounds: for example, titanium tetraacetylacetonate, etc. VII) Titanium ester coupling agent: for example, isopropyl tridodecylbenzenesulfonyl titanium ester, etc.

Among them, as an organic titanium compound, from the viewpoint of exerting better drug resistance, at least one compound selected from the group including I) titanium chelate compounds, II) tetraalkoxy titanium compounds and III) dioctenyl titanium compounds is preferred. In particular, bis(ethylacetyl acetate)diisopropoxytitanium, tetra(n-butoxy)titanium and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.

When an organic titanium compound is added, the amount thereof is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, the obtained hardened pattern exhibits good heat resistance and chemical resistance, while when the amount is 10 parts by mass or less, the storage stability of the composition is excellent.

[Antioxidant] The composition of the present invention may contain an antioxidant. By containing an antioxidant as an additive, the ductility of the film after curing or the adhesion to the metal material can be improved. As the antioxidant, phenol compounds, phosphite compounds, thioether compounds, etc. can be cited. As the phenol compound, any phenol compound known as a phenolic antioxidant can be used. As a preferred phenol compound, a hindered phenol compound can be cited. Compounds having a substituent at a position adjacent to a phenolic hydroxyl group (adjacent position) are preferred. As the aforementioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. In addition, the antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenol)ethyl phosphite. As commercially available antioxidants, for example, ADKSTAB AO-20, ADKSTAB AO-30, ADKSTAB AO-40, ADKSTAB AO-50, ADKSTAB AO-50F, ADKSTAB AO-60, ADKSTAB AO-60G, ADKSTAB AO-80, ADKSTAB AO-330 (all manufactured by ADEKA CORPORATION) etc. can be cited. In addition, the antioxidant can also use the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967. In addition, the composition of the present invention can contain a potential antioxidant as needed. As potential antioxidants, there can be cited compounds in which the site that functions as an antioxidant is protected by a protecting group, and the protecting group is released by heating at 100 to 250°C or heating at 80 to 200°C in the presence of an acid/base catalyst, thereby functioning as an antioxidant. As potential antioxidants, there can be cited compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Publication No. 2017-008219. As commercially available products of potential antioxidants, there can be cited ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like. Preferred examples of antioxidants include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol and compounds represented by the general formula (3).

[Chemical formula 58]

In the general formula (3), ^R5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, ^R6 represents an alkylene group having 2 or more carbon atoms, ^R7 represents an alkylene group having 2 or more carbon atoms, or a monovalent to tetravalent organic group containing at least one of an O atom and a N atom. k represents an integer of 1 to 4.

The compound represented by the general formula (3) inhibits the oxidative degradation of the aliphatic group or the phenolic hydroxyl group of the resin. In addition, it can inhibit the oxidation of the metal by its rust-proofing effect on the metal material.

Since it can act on the resin and the metal material simultaneously, k is preferably an integer of 2 to 4. R ⁷ includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkyl silyl group, an alkoxy silyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, a combination thereof, and the like, and may further have a substituent. Among them, from the viewpoint of solubility in a developer or metal adhesion, alkyl ether and -NH- are preferred, and from the viewpoint of interaction with the resin and metal adhesion by metal complex formation, -NH- is more preferred.

Examples of the compound represented by the following general formula (3) include the following, but are not limited to the following structure.

[Chemical formula 59]

[Chemical formula 60]

[Chemical formula 61]

[Chemical formula 62]

The amount of antioxidant added is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight relative to the resin. When the amount added is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the ductility characteristics after the reliability test or the adhesion to the metal material. When the amount added is more than 10 parts by weight, the sensitivity of the resin composition may decrease due to the interaction with the photosensitive agent. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

<Restrictions on other contained substances> From the perspective of coating surface properties, the water content of the curable resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, and even more preferably less than 0.6 mass%. Methods for maintaining the water content include adjusting the humidity under storage conditions, reducing the porosity of the storage container, etc.

From the perspective of insulation, the metal content of the hardening resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel, and the like. When multiple metals are included, the total of the metals is preferably within the above range.

In addition, as a method for reducing the metal impurities unintentionally contained in the hardening resin composition of the present invention, the following methods can be cited: selecting a raw material with a low metal content as a raw material constituting the hardening resin composition of the present invention; filtering the raw material constituting the hardening resin composition of the present invention with a filter; lining with polytetrafluoroethylene or the like in an apparatus to perform distillation under conditions that suppress contamination as much as possible.

In the curable resin composition of the present invention, if the use as a semiconductor material is considered, from the viewpoint of wiring corrosion, the content of halogen atoms is preferably less than 500 mass ppm, less than 300 mass ppm is more preferably, and less than 200 mass ppm is further preferably. Among them, the content of halogen ions is preferably less than 5 mass ppm, less than 1 mass ppm is more preferably, and less than 0.5 mass ppm is further preferably. As halogen atoms, chlorine atoms and bromine atoms can be cited. It is preferred that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, are respectively within the above ranges. As a method for adjusting the content of halogen atoms, ion exchange treatment can be preferably cited.

As a container for storing the curable resin composition of the present invention, a conventionally known container can be used. In addition, as a container, in order to suppress the mixing of impurities into the raw materials or the curable composition, it is also preferable to use a multi-layer bottle having an inner wall composed of six types of six layers of resin or a bottle having a seven-layer structure made of six types of resin. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

<Application of the curable resin composition> The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a redistribution layer. In addition, it can also be used for forming an insulating film of a semiconductor device or forming a stress buffer film, etc.

<Preparation of hardening resin composition> The hardening resin composition of the present invention can be prepared by mixing the above-mentioned components. The mixing method is not particularly limited and can be carried out by a conventionally known method.

Furthermore, in order to remove foreign matter such as dust or particles in the curable resin composition, it is preferred to perform filtering using a filter. The pore size of the filter is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.1 μm or less. On the other hand, from the perspective of productivity, 5 μm or less is preferred, 3 μm or less is more preferred, and 1 μm or less is further preferred. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be pre-cleaned with an organic solvent. In the filter filtering process, multiple filters may be connected in series or in parallel. When using multiple filters, filters with different pore sizes or materials can be used in combination. Also, various materials can be filtered multiple times. When filtering multiple times, it can be cycle filtering. Also, filtering can be performed by pressurization. When filtering is performed by pressurization, the pressurization pressure is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the perspective of productivity, 0.01MPa or more and 1.0MPa or less is preferred, 0.03MPa or more and 0.9MPa or less is more preferred, and 0.05MPa or more and 0.7MPa or less is further preferred. In addition to filtering using a filter, impurity removal using an adsorbent can also be performed. Filtering using a filter and impurity removal using an adsorbent can also be combined. As the adsorbent, a known adsorbent can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be cited.

(Curing film, laminate, semiconductor device, and method for manufacturing the same) Next, the curing film, laminate, semiconductor device, and method for manufacturing the same are explained.

The cured film of the present invention is a cured film formed by curing the resin composition of the present invention. The cured film is preferably a patterned cured film. The film thickness of the cured film of the present invention can be set to, for example, 0.5 μm or more, or 1 μm or more. In addition, as an upper limit, it can be set to 100 μm or less, or 30 μm or less.

The cured film of the present invention can be laminated with more than 2 layers, and further 3 to 7 layers to form a laminate. The laminate of the present invention preferably includes more than 2 layers of cured film and a metal layer between any of the above-mentioned cured films. For example, as a preferred embodiment, a laminate having a layered structure including at least three layers of a first cured film, a metal layer, and a second cured film laminated in sequence can be cited. The above-mentioned first cured film and the above-mentioned second cured film are both the cured films of the present invention. As a preferred embodiment, for example, the above-mentioned first cured film and the above-mentioned second cured film are both films formed by curing the resin composition of the present invention. The resin composition of the present invention used to form the first cured film and the resin composition of the present invention used to form the second cured film may have the same composition or different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring such as a redistribution layer.

Examples of fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc. In addition, examples include patterning of sealing films, substrate materials (base films or cover films of flexible printed circuit boards, interlayer insulating films), or insulating films for packaging purposes as described above by etching. For the use of these, for example, you can refer to SCIENCE AND TECHNOLOGY CO., LTD. "Advanced Functionality and Application Technology of Polyimide" April 2008, supervised by Masaaki Kakimoto, CMC Technical Library "Basics and Development of Polyimide Materials" November 2011, Japan Polyimide and Aromatic Polymer Research Association/ed. "Latest Polyimide Fundamentals and Applications" NTS Inc., August 2010, etc.

Furthermore, the cured film of the present invention can also be used in the production of printing plates such as offset printing plates and screen printing plates, in the etching of molded components, in the production of protective varnishes and dielectric layers in electronics, especially microelectronics, and the like.

The method for producing a cured film of the present invention (hereinafter, also referred to as "the method for producing the present invention") preferably includes a film forming process of applying the resin composition of the present invention to a substrate to form a film (resin film). The method for producing a cured film of the present invention preferably includes the above-mentioned film forming process, an exposure process of exposing the above-mentioned film, and a development process of developing the above-mentioned film. By the above-mentioned exposure process and development process, a pattern of the cured film can be obtained. Furthermore, the method for producing a cured film of the present invention preferably includes the above-mentioned film forming process and the above-mentioned development process as needed, and includes a heating process of heating the above-mentioned film at 50 to 450°C. Specifically, the process including the following (a) to (d) is also preferred. (a) A film forming process of applying a resin composition to a substrate to form a film (resin composition layer) (b) An exposure process of exposing the film after the film forming process (c) A developing process of developing the exposed film (d) A heating process of heating the developed film at 50 to 450°C By heating in the heating process, the resin layer hardened by exposure can be further hardened. In the heating process, for example, the hot alkali generator decomposes to obtain sufficient hardening properties.

The method for manufacturing a laminated body of a preferred embodiment of the present invention includes the method for manufacturing a cured film of the present invention. After forming a cured film according to the above-mentioned method for manufacturing a laminated body of the present embodiment, the process (a) or the processes (a) to (c) or the processes (a) to (d) are further performed again. In particular, it is preferred to perform the above-mentioned processes in sequence a plurality of times, for example 2 to 5 times (that is, a total of 3 to 6 times). By laminating the cured film in this way, a laminated body can be manufactured. In the present invention, it is particularly preferred to provide a metal layer on a portion provided with a cured film or between cured films, or on a portion provided with a cured film and between cured films. In addition, when manufacturing a laminate, it is not necessary to repeat all the processes (a) to (d). As described above, a laminate of a cured film can be obtained by performing at least (a), preferably (a) to (c) or (a) to (d) a plurality of times.

<Film-forming process (layer-forming process)> The manufacturing method of the preferred embodiment of the present invention includes a film-forming process (layer-forming process) of applying a resin composition to a substrate to form a film (layer).

The type of substrate can be appropriately specified according to the purpose, and can be semiconductor substrates such as silicon, silicon nitride, polycrystalline silicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, evaporated film, magnetic film, reflective film, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrate, electrode plate of plasma display panel (PDP), etc., without special restrictions. In addition, these substrates can be provided with a layer such as a close contact layer or an oxide layer on the surface. In the present invention, semiconductor substrates are particularly preferred, and silicon substrates, Cu substrates and mold substrates are more preferred. In addition, the substrate may have a bonding layer or an oxide layer formed of hexamethyldisilazane (HMDS) or the like on the surface. In addition, as the substrate, for example, a plate-shaped substrate (substrate) may be used. The shape of the substrate is not particularly limited, and may be circular or rectangular, but a rectangular shape is preferred. As for the size of the substrate, if it is circular, for example, the diameter is 100 to 450 mm, preferably 200 to 450 mm. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.

Furthermore, when a resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer becomes a base material.

As a method of applying the resin composition to the substrate, coating is preferred.

Specifically, as the applicable method, there can be exemplified dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of the uniformity of the thickness of the resin composition layer, spin coating, slit coating, spray coating, and inkjet coating are more preferred. By appropriately adjusting the solid component concentration or coating conditions according to the method, a resin layer of a desired thickness can be obtained. Furthermore, the coating method can be appropriately selected according to the shape of the substrate. For a circular substrate such as a wafer, spin coating, spray coating, inkjet coating, etc. are preferred, and for a rectangular substrate, slit coating, spray coating, inkjet coating, etc. are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. In addition, a method of transferring a coating film previously applied by the above-mentioned applying method and formed on a temporary support to a substrate can also be applied. Furthermore, depending on the viscosity of the photosensitive resin composition or the film thickness to be set, it is also preferable to apply the rotation speed of 300 to 3,500 rpm for 10 to 180 seconds. Moreover, in order to obtain uniform film thickness, multiple rotation speeds can also be combined for coating. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of Japanese Patent Publication No. 2006-023696 or paragraphs 0096 to 0108 of Japanese Patent Publication No. 2006-047592 can also be preferably used in the present invention. Furthermore, a process for removing excess film can be performed at the end of the substrate. Examples of such processes include edge beading residue rinsing (EBR), air knife, back rinse, etc. In addition, the following pre-wetting process can also be adopted: before applying the resin composition to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.

<Drying process> The manufacturing method of the present invention may include a drying process for removing the solvent after the film forming process (layer forming process). The preferred drying temperature is 50 to 150°C, 70 to 130°C is more preferred, and 90 to 110°C is further preferred. The drying time may be 30 seconds to 20 minutes, 1 minute to 10 minutes is preferred, and 3 minutes to 7 minutes is more preferred.

<Exposure process> The manufacturing method of the present invention may include an exposure process for exposing the above-mentioned film (resin composition layer). The exposure amount is not particularly specified as long as it can cure the resin composition. For example, based on the exposure energy conversion at a wavelength of 365nm, 100 to 10,000mJ/ ^cm2 is preferably irradiated, and 200 to 8,000mJ/ ^cm2 is more preferably irradiated.

The exposure wavelength can be appropriately set within the range of 190 to 1,000 nm, preferably 240 to 550 nm. In addition, the exposure light preferably includes light with a wavelength of 365 nm or a wavelength of 405 nm, and more preferably includes light with a wavelength of 405 nm.

If we explain the exposure wavelength in relation to the light source, we can cite (1) semiconductor lasers (wavelengths of 830nm, 532nm, 488nm, 405nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-rays (wavelength 436nm), h-rays (wavelength 405nm), i-rays (wavelength 365nm), wide (three wavelengths of g, h, and i-rays), (4) excimer lasers, KrF excimer lasers (wavelength 248nm), ArF excimer lasers (wavelength 193nm), F2 excimer lasers (wavelength 157nm), (5) extreme ultraviolet light; EUV (wavelength 13.6nm), (6) electron beams, and (7) the second harmonic of the YAG laser is 532nm and the third harmonic is 355nm. For the resin composition of the present invention, exposure based on a high-pressure mercury lamp is particularly preferred, and exposure based on i-rays is particularly preferred. In this way, high exposure sensitivity can be obtained. In addition, from the perspective of operation and productivity, a wide (3 wavelengths of g, h, and i-rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is also preferred.

In addition, there is no particular limitation on the exposure method, as long as at least a portion of the film (photosensitive film) composed of the curable resin composition is exposed, examples of which include exposure using a photomask and exposure based on a laser direct imaging method. In the present invention, the exposure in the exposure process is based on a laser direct imaging method, which is also one of the preferred aspects.

<Developing process> The manufacturing method of the present invention may include a developing process for developing (developing) the exposed film (resin composition layer). The unexposed portion (non-exposed portion) is removed by developing. The developing method is not particularly limited as long as the desired pattern can be formed. For example, it can be cited that the developer is sprayed from a nozzle, sprayed with a mist, and the substrate is immersed in the developer. Spraying from a nozzle can be preferably used. In the developing process, a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially stationary state, a process of vibrating the developer with ultrasound, etc., and a process of combining these can be adopted.

Development is performed using a developer. The developer can be used without particular restrictions as long as it can remove the unexposed portion (non-exposed portion). As the developer, a developer containing an organic solvent or an alkaline aqueous solution can be used.

In the present invention, the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained by inputting a structural formula into ChemBioDraw as a calculated value.

When the developer contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxy acetates (e.g., methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g., methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate), , ethyl ethoxylate, etc.)), 3-alkoxy alkyl propionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkoxy alkyl propionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.) ethyl ester)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like, and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol dimethyl ether, Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc. are preferably exemplified, and, as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. are preferably exemplified, as sulfoxides, for example, dimethyl sulfoxide is preferably exemplified, and, further, a mixture of these organic solvents is also preferably exemplified.

When the developer contains an organic solvent, in the present invention, cyclopentanone and γ-butyrolactone are preferred, and cyclopentanone is more preferred. In addition, when the developer contains an organic solvent, the organic solvent can be used alone or in combination of two or more.

When the developer contains an organic solvent, preferably 50% by mass or more of the developer is the organic solvent, more preferably 70% by mass or more of the developer is the organic solvent, and even more preferably 90% by mass or more of the developer is the organic solvent. In addition, the developer may contain 100% by mass of the organic solvent.

The developer may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be cited.

When the developer is an alkaline aqueous solution, examples of the alkaline compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate, etc. TMAH is preferred. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass %, more preferably 0.1 to 5 mass %, and even more preferably 0.3 to 3 mass % in the total mass of the developer.

[Developer supply method] The developer supply method is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the developer, using a nozzle to supply the developer to the substrate by immersion development, or continuously supplying the developer. The type of nozzle is not particularly limited, and vertical nozzles, shower nozzles, spray nozzles, etc. can be cited. From the perspective of developer permeability, non-image removal, and manufacturing efficiency, the method of supplying the developer with a vertical nozzle or the method of continuously supplying with a spray nozzle is preferred. From the perspective of developer permeability to the image area, the method of supplying with a spray nozzle is more preferred. In addition, a process can be adopted in which the developer is continuously supplied with a vertical nozzle, the substrate is rotated to remove the developer from the substrate, and after spin drying, the developer is continuously supplied with a vertical nozzle again, and the substrate is rotated to remove the developer from the substrate, and this process can be repeated multiple times. In addition, as a method for supplying the developer in the developing process, a process of continuously supplying the developer to the substrate, a process of keeping the developer on the substrate in a substantially stationary state, a process of vibrating the developer on the substrate using ultrasound or the like, and a process combining these processes can be adopted.

The developing time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution during the developing process is not particularly specified, but can generally be carried out at 10 to 45°C, preferably 20 to 40°C.

After the treatment using the developer, rinsing can be further performed. It is preferable to perform rinsing in a solvent different from the developer. For example, the solvent contained in the resin composition can be used for rinsing. When the developer is a developer containing an organic solvent, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol), etc. can be cited as the rinsing liquid, and PGMEA is preferred. In addition, as a rinsing liquid for development based on a developer containing an alkaline aqueous solution, water is preferred. The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 5 seconds to 1 minute. The temperature of the rinse solution during rinsing is not particularly specified, but can be preferably performed at 10 to 45°C, more preferably 18 to 30°C.

When the rinsing liquid contains an organic solvent, the organic solvent may be preferably esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., 3-alkoxypropionic acid methyl ester, 3-alkoxypropionic acid ethyl ester, etc. (for example, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-alkoxy propionic acid alkyl esters (for example: 2-alkoxypropionic acid methyl ester, 2-alkoxypropionic acid ethyl ester, 2-alkoxypropionic acid propyl ester, etc. (for example, 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2-ethoxypropionic acid methyl ester, 2-ethoxypropionic acid ethyl ester)), 2-alkoxy-2-methylpropionic acid methyl ester and 2-alkoxy-2-methylpropionic acid ethyl ester (for example, 2-methoxy-2- The ethers include, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl thiocyanate, ethyl thiocyanate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate. Esters, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and, as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and, as sulfoxides, for example, dimethyl sulfoxide, and, as alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, triethylene glycol, etc., and, as amides, N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

When the rinsing liquid contains an organic solvent, the organic solvent can be used alone or in combination of two or more. In the present invention, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME are particularly preferred, cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME are more preferred, and cyclohexanone and PGMEA are further preferred.

When the rinse liquid contains an organic solvent, preferably 50 mass % or more of the rinse liquid is the organic solvent, more preferably 70 mass % or more of the rinse liquid is the organic solvent, and even more preferably 90 mass % or more of the rinse liquid is the organic solvent. In addition, the rinse liquid may contain 100 mass % of the organic solvent.

The rinse solution may further contain other components. As other components, for example, a known surfactant or a known defoaming agent can be cited.

[Method for supplying rinse liquid] The method for supplying rinse liquid is not particularly limited as long as the desired pattern can be formed. There are methods of immersing the substrate in the rinse liquid, immersion development on the substrate, supplying the rinse liquid to the substrate with a shower, and continuously supplying the developer to the substrate using a mechanism such as a vertical nozzle. From the perspective of the permeability of the rinse liquid, the removal of the non-image part, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a vertical nozzle, a spray nozzle, etc. The method of continuously supplying using a spray nozzle is preferred, and from the perspective of the permeability of the rinse liquid to the image part, the method of supplying using a spray nozzle is more preferred. There is no particular limitation on the type of nozzle, and examples include vertical nozzles, shower nozzles, and mist nozzles. That is, the rinsing process is preferably a process in which a rinsing liquid is supplied or continuously supplied to the film after exposure using a vertical nozzle, and a process in which a mist nozzle is used to supply the rinsing liquid is more preferably used. In addition, as a method for supplying the developer in the rinsing process, a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept substantially stationary on the substrate, a process in which the rinsing liquid is vibrated on the substrate using ultrasound or the like, and a process in which these are combined can be used.

<Heating process> The manufacturing method of the present invention preferably includes a process (heating process) of heating the developed film at 50 to 450°C. It is preferred to include a heating process after the film formation process (layer formation process), drying process and development process. In the heating process, for example, a cyclization reaction of a precursor of a specific resin is carried out by generating an alkali by decomposing the above-mentioned hot alkali generator. In addition, the resin composition of the present invention may contain a free radical polymerizing compound other than a precursor of a specific resin, and the curing of the unreacted free radical polymerizing compound other than a precursor of a specific resin can also be carried out in the process. The heating temperature (maximum heating temperature) of the layer in the heating process is preferably 50°C or higher, more preferably 80°C or higher, further preferably 140°C or higher, further preferably 150°C or higher, further preferably 160°C or higher, and further preferably 170°C or higher. As the upper limit, 500°C or lower is preferably, 450°C or lower is more preferably, 350°C or lower is further preferably, 250°C or lower is further preferably, and 220°C or lower is further preferably.

The heating is preferably performed at a heating rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min. By setting the heating rate to 1°C/min or more, productivity can be ensured while preventing excessive volatility of amines, and by setting the heating rate to 12°C/min or less, the residual stress of the cured film can be reduced. Furthermore, in the case of an oven capable of rapid heating, the heating rate is preferably performed at a heating rate of 1 to 8°C/sec from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.

The temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The temperature at the start of heating refers to the temperature at the start of the process of heating to the maximum heating temperature. For example, when a resin composition is applied to a substrate and then dried, it refers to the temperature of the dried film (layer), and it is preferably to gradually increase the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and further preferably 30 to 240 minutes.

In particular, when a multi-layer laminate is formed, from the viewpoint of the adhesion between the layers of the cured film, the heating temperature is preferably 180°C to 320°C, and more preferably 180°C to 260°C. Although the reason is not clear, it is believed that the acetylene groups of the specific resin between the layers undergo cross-linking reactions at this temperature.

Heating can be performed in stages. For example, the following pretreatment process can be performed: heating from 25°C to 180°C at 3°C/min, maintaining at 180°C for 60 minutes, heating from 180°C to 200°C at 2°C/min, and maintaining at 200°C for 120 minutes. The heating temperature of the pretreatment process is preferably 100-200°C, more preferably 110-190°C, and even more preferably 120-185°C. In the pretreatment process, as described in the specification of U.S. Patent No. 9159547, it is also preferred to perform the treatment while irradiating with ultraviolet rays. By this pretreatment process, the properties of the membrane can be further improved. The pretreatment process can be performed in a short time of about 10 seconds to 2 hours, preferably 15 seconds to 30 minutes. The pretreatment can also be set as a step of more than two stages, for example, pretreatment process 1 can be performed in the range of 100 to 150°C, and then pretreatment process 2 can be performed in the range of 150 to 200°C.

The heating and cooling can be further performed, and the cooling speed at this time is preferably 1 to 5°C/minute.

From the perspective of preventing the decomposition of a specific resin, it is better to perform the heating process in an atmosphere with a low oxygen concentration by flowing inert gases such as nitrogen, helium, and argon. The oxygen concentration is preferably 50ppm (volume ratio) or less, and more preferably 20ppm (volume ratio) or less. The heating mechanism is not particularly limited, and examples thereof include a heating plate, an infrared furnace, an electric oven, a hot air oven, and the like.

<Metal layer forming process> The manufacturing method of the present invention preferably includes a metal layer forming process for forming a metal layer on the surface of the film (resin composition layer) after development.

The metal layer is not particularly limited, and existing metals can be used, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper, aluminum, and alloys containing these metals are more preferred, and copper is further preferred.

The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Table No. 2001-521288, Japanese Patent Publication No. 2004-214501, and Japanese Patent Publication No. 2004-101850 can be applied. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and methods combining these methods can be considered. More specifically, a patterning method combining sputtering, photolithography, and etching, and a patterning method combining photolithography and electrolytic plating can be cited.

The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm at the thickest wall portion.

<Layering process> The manufacturing method of the present invention preferably further includes a layering process.

The lamination process includes a series of processes including (a) film formation process (layer formation process), (b) exposure process, (c) development process, and (d) heating process, which are performed again in order on the surface of the hardened film (resin layer) or metal layer. However, it is also possible to perform only (a) film formation process repeatedly. In addition, it is also possible to perform (d) heating process at the end or in the middle of the lamination. That is, it is possible to perform (a) to (c) processes repeatedly for a specified number of times, and then perform (d) heating, thereby hardening the deposited resin composition layer. Furthermore, after the (c) developing process, the (e) metal layer forming process may be included. At this time, the heating in (d) may be performed each time, or the heating in (d) may be performed all at once after the layering is performed a specified number of times. Of course, the layering process may further appropriately include the above-mentioned drying process or heating process.

When a further layering process is performed after the layering process, a surface activation treatment process may be further performed after the heating process, after the exposure process, or after the metal layer forming process. As the surface activation treatment, plasma treatment may be exemplified.

The above-mentioned lamination process is preferably performed 2 to 20 times, 2 to 5 times, and 3 to 5 times. In addition, each layer in the lamination process can be the same layer in composition, shape, film thickness, etc., or different layers.

For example, a structure of resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, in which the number of resin layers is 2 or more and 20 or less is preferred, a structure of 3 or more and 7 or less is more preferred, and a structure of 3 or more and 5 or less is further preferred.

In the present invention, after the metal layer is provided, it is preferred to further form a hardened film (resin layer) of the resin composition so as to cover the metal layer. Specifically, it is possible to cite an embodiment in which (a) film forming process, (b) exposure process, (c) development process, (e) metal layer forming process, and (d) heating process are repeated in this order, or an embodiment in which (a) film forming process, (b) exposure process, (c) development process, and (e) metal layer forming process are repeated in this order and (d) heating process is provided at the end or in the middle. By alternately performing a lamination process of a resin composition layer (resin layer) and a metal layer forming process, it is possible to alternately laminarize a resin composition layer (resin layer) and a metal layer.

(Surface activation treatment process) The method for manufacturing a laminate of the present invention may include a surface activation treatment process for performing surface activation treatment on at least a portion of the above-mentioned metal layer and the photosensitive resin composition layer. The surface activation treatment process is usually performed after the metal layer forming process, but the metal layer forming process may also be performed after the above-mentioned exposure and development process and after the photosensitive resin composition layer is subjected to the surface activation treatment process. The surface activation treatment may be performed only on at least a portion of the metal layer, may be performed only on at least a portion of the exposed photosensitive resin composition layer, or may be performed separately on at least a portion of both the metal layer and the exposed photosensitive resin composition layer. It is preferred to perform surface activation treatment on at least a portion of the metal layer, and it is preferred to perform surface activation treatment on a portion or all of the region of the metal layer where the photosensitive resin composition layer is formed on the surface. In this way, by performing surface activation treatment on the surface of the metal layer, the adhesion with the resin layer disposed on the surface can be improved. In addition, it is preferred to perform surface activation treatment on a portion or all of the photosensitive resin composition layer (resin layer) after exposure. In this way, by performing surface activation treatment on the surface of the photosensitive resin composition layer, the adhesion with the metal layer or resin layer disposed on the surface subjected to surface activation treatment can be improved. Specifically, the surface activation treatment includes plasma treatment selected from various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment based on _CF4 / _O2 , _NF3 / _O2 , _SF6 , _NF3 , _NF3 / _O2 , surface treatment based on ultraviolet (UV) ozone method, treatment of removing oxide film by immersion in hydrochloric acid aqueous solution and then immersion in an organic surface treatment agent containing a compound having at least one of an amino group and a thiol group, and mechanical roughening treatment using a brush. Plasma treatment is preferred, and oxygen plasma treatment using oxygen as the raw material gas is particularly preferred. In the case of corona discharge treatment, the energy is preferably 500-200,000 J/ ^m2 , more preferably 1000-100,000 J/ ^m2 , and most preferably 10,000-50,000 J/ ^m2 .

The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. As a specific example of a semiconductor device in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer, reference can be made to paragraphs 0213 to 0218 and FIG. 1 of Japanese Patent Publication No. 2016-027357, which are incorporated into this specification. [Example]

The present invention is further specifically described below with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.

<Synthesis Example 1: Synthesis of polymer A-1> 23.48 g of 4,4'-oxydiphthalic acid dianhydride (ODPA) and 22.27 g of 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA) were placed in a separation flask, and 39.69 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and stirred at room temperature. While stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction was terminated, it was naturally cooled to room temperature and left at room temperature for 16 hours. Next, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice cooling, and then 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added, and stirring was continued for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 716.21 g of ethanol to generate a precipitate consisting of a crude polymer. The resulting crude polymer was filtered out and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer. The precipitate was filtered out and then vacuum dried to obtain a powdered polymer (polyimide precursor) A-1. The molecular weight of the polymer A-1 was measured by gel permeation chromatography (standard polystyrene conversion), and the weight average molecular weight (Mw) was 20,000.

<Synthesis Example 2: Synthesis of Polymer A-2> Polymer A-2 was synthesized by the same method as Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 46.96 g of ODPA.

<Synthesis Example 3: Synthesis of Polymer A-3> Polymer A-3 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were replaced with 46.96 g of ODPA, and 39.69 g of HEMA were replaced with 19.85 g of HEMA and 18.32 g of diethylene glycol monomethyl ether.

<Synthesis Example 4: Synthesis of polymer A-4> In a dry reactor equipped with a stirrer, a condenser, and a flat-bottomed joint equipped with an internal thermometer, 10.65 g (50 mmol) of 4,6-dihydroxy-1,3-phenylenediamine dihydrochloride was dissolved in 85.8 g of N-methylpyrrolidone (NMP) while removing water. Then, 9.74 g (48 mmol) of terephthalic acid chloride dissolved in 55.0 g of NMP was dripped over 1 hour and stirred at 25°C for 2 hours. After stirring, it was precipitated in 2 liters of water/methanol = 75/25 (volume ratio) and stirred at 2,000 rpm for 30 minutes. The precipitated polybenzophenone precursor resin was removed by filtration and washed with 1.5 liters of water. The obtained resin was dried at 40°C under reduced pressure for 1 day to obtain A-4.

<Synthesis Example 5: Synthesis of Polymer A-5> 29.08 g of trimellitic anhydride was added to a separation flask, 19.85 g of 2-hydroxyethyl methacrylate (HEMA) and 136.83 g of γ-butyrolactone were added, and the mixture was stirred at room temperature. While stirring, 24.66 g of pyridine was added to obtain a reaction mixture. After the heat generated by the reaction was terminated, the mixture was naturally cooled to room temperature and left at room temperature for 16 hours. Next, a solution of 62.46 g of dicyclohexylcarbodiimide (DCC) dissolved in 61.57 g of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring under ice cooling, and then 27.42 g of 4,4'-diaminodiphenyl ether (DADPE) suspended in 119.73 g of γ-butyrolactone was added over 60 minutes while stirring. After further stirring at room temperature for 2 hours, 7.17 g of ethanol was added, and stirring was continued for 1 hour, and then 136.83 g of γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution. The obtained reaction solution was added to 716.21 g of ethanol to generate a precipitate consisting of a crude polymer. The resulting crude polymer was filtered out and dissolved in 403.49 g of tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was added dropwise to 8470.26 g of water to precipitate the polymer, and the resulting precipitate was filtered out and vacuum dried to obtain a powdery polymer (polyamide imide precursor) A-5.

<Synthesis Example 6: Synthesis of Polymer A-6> Polymer A-6 was synthesized by the same method as Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were changed to 44.54 g of BPDA.

<Synthesis Example 7: Synthesis of Polymer A-7> Polymer A-7 was synthesized by the same method as in Synthesis Example 1 except that 23.48 g of ODPA and 22.27 g of BPDA were replaced with 46.96 g of ODPA, and 39.69 g of HEMA was replaced with 52.52 g of the compound represented by the following formula (7-1). [Chemical Formula 63]

<Examples and Comparative Examples> In each example, the components listed in the following table were mixed to obtain each curable resin composition. In each comparative example, the components listed in the following table were mixed to obtain each comparative composition. Specifically, the content of each component listed in Tables 1 to 7 was set to the amount (mass parts) listed in the brackets of each column of Tables 1 to 7. However, regarding the content of the specific compound, the content of the specific compound relative to the total mass of the composition was set to the value listed in the column of "Specific compound content (ppm)". The obtained curable resin composition and comparative composition were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.8μm. In Tables 1 to 7, the entry "-" indicates that the composition does not contain the component.

[Table 1] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 1 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 50 NMP (45.1) EL (11.3) M 405 Negative B A 2 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-2 50 NMP (45.1) EL (11.3) M 405 Negative B A 3 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-3 50 NMP (45.1) EL (11.3) M 405 Negative B A 4 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-4 50 NMP (45.1) EL (11.3) M 405 Negative B A 5 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 6 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-6 50 NMP (45.1) EL (11.3) M 405 Negative B A 7 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-7 50 NMP (45.1) EL (11.3) M 405 Negative B A 8 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-8 50 NMP (45.1) EL (11.3) M 405 Negative B A 9 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-9 50 NMP (45.1) EL (11.3) M 405 Negative B A 10 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-10 50 NMP (45.1) EL (11.3) M 405 Negative B A 11 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-ll 50 NMP (45.1) EL (11.3) M 405 Negative B A 12 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-12 50 NMP (45.1) EL (11.3) M 405 Negative B A 13 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-13 50 NMP (45.1) EL (11.3) M 405 Negative B A 14 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-14 50 NMP (45.1) EL (11.3) M 405 Negative B A 15 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-15 50 NMP (45.1) EL (11.3) M 405 Negative B A

[Table 2] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 16 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-16 50 NMP (45.1) EL (11.3) M 405 Negative B A 17 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-17 50 NMP (45.1) EL (11.3) M 405 Negative B A 18 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-18 50 NMP (45.1) EL (11.3) M 405 Negative B A 19 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-19 50 NMP (45.1) EL (11.3) M 405 Negative B A 20 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-20 50 NMP (45.1) EL (11.3) M 405 Negative B A twenty one A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-21 50 NMP (45.1) EL (11.3) M 405 Negative B A twenty two A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-22 50 NMP (45.1) EL (11.3) M 405 Negative B A twenty three A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-23 50 NMP (45.1) EL (11.3) M 405 Negative B A twenty four A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-24 50 NMP (45.1) EL (11.3) M 405 Negative B A 25 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-25 50 NMP (45.1) EL (11.3) M 405 Negative B A 26 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-26 50 NMP (45.1) EL (11.3) M 405 Negative B A 27 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-27 50 NMP (45.1) EL (11.3) M 405 Negative B A 28 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 10 NMP (45.1) EL (11.3) M 405 Negative B A 29 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 100 NMP (45.1) EL (11.3) M 405 Negative B A 30 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 1000 NMP (45.1) EL (11.3) M 405 Negative A A

[Table 3] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 31 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 10000 NMP (45.1) EL (11.3) M 405 Negative A A 32 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50000 NMP (45.1) EL (11.3) M 405 Negative B A 33 A-1 (35) B-1 (1.4) - X-2 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B B 34 A-1 (35) B-1 (1.4) - X-3 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 35 A-2 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 36 A-3 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 37 A-4 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 38 A-5 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 39 A-1 (35) B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 40 A-1 (35) B-3 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 41 A-1 (35) B-1 (0.7) B-2 (0.7) X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 42 A-1 (35) B-1 (1.4) - X-1 (1.0) C-2 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 43 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 44 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 45 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A

[Table 4] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 46 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 47 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 48 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) - - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 49 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) - E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 50 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-2 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 51 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-3 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 52 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-4 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 53 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-5 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 54 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 DMSO (11.3) γBL (45.1) M 405 Negative B A 55 A-1 (50) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 56 A-1 (35) B-1 (3.0) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 57 A-1 (35) B-1 (1.4) - X-1 (2.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 58 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (6.8) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 59 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.4) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 60 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (4.8) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A

[Table 5] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 61 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (1.8) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 62 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (2.0) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 63 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (11.3) EL (45.1) M 405 Negative B A 64 A-1 (35) - - X-1 (2.4) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B B 65 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) D 405 Negative B A 66 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) D 405 Negative B A 67 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 50 NMP (45.1) EL (11.3) M 405 Negative B A G-5 50 G-9 50 68 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-1 50 NMP (45.1) EL (11.3) M 405 Negative A A G-5 1000 G-9 50 69 A-1 (35) B-1 (1.4) - X-1/X-2 (1.0/1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 70 A-2/A-6 (18/18) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 71 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 72 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-6 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 73 A-1 (35) B-1 (1.4) - X-4 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 74 A-1 (35) B-1 (1.4) - X-5 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A

[Table 6] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 75 A-1 (35) B-1 (1.4) - X-6 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 76 A-1 (35) B-1 (1.4) - X-7 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 77 A-1 (35) B-1 (1.4) - X-9 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 78 A-2 (35) B-2 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-3 (2.4) - - F-3 (0.7) G-5 50 DMSO (11.3) γBL (45.1) M 405 Negative B A 79 A-7 (35) - - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 just B A 80 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 81 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 82 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 83 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-3 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 84 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-4 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 85 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-5 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 86 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-6 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 87 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-7 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 405 Negative B A 88 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 365 Negative B A 89 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 1000 NMP (45.1) EL (11.3) M 365 Negative A A

[Table 7] Resin Photosensitizer Organometallic complexes Crosslinking agent Polymerization inhibitor Additives Metal Adhesion Improver Specific compounds Solvent Exposure conditions Exposure wavelength (nm) Development conditions Resolution Sensitivity Type Content (ppm) Embodiment 90 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-2 (0.2) E-1 (2.4) E-2 (0.9) E-6 (0.2) F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 365 Negative B A 91 A-7 (35) - - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-4 (2.4) E-5 (0.5) - F-1 (0.7) G-5 50 NMP (45.1) EL (11.3) M 365 just B A Comparison Example 1 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 0 NMP (45.1) EL (11.3) M 405 Negative D C 2 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 5 NMP (45.1) EL (11.3) M 405 Negative D C 3 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 60000 NMP (45.1) EL (11.3) M 405 Negative C B 4 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 100000 NMP (45.1) EL (11.3) M 405 Negative D C 5 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 0 NMP (45.1) EL (11.3) D 405 Negative D C 6 A-1 (35) B-1 (1.4) - X-1 (1.0) C-1 (3.4) D-1 (0.2) E-1 (2.4) E-2 (0.9) - F-1 (0.7) G-5 60000 NMP (45.1) EL (11.3) D 405 Negative C B

The details of each component listed in Tables 1 to 7 are as follows.

[Resin] •A-1 to A-7: polymers A-1 to A-7 obtained by the above synthesis example

[Photosensitive agent (photoradical polymerization initiator)] •B-1 to B-3: Compounds with the following structure [Chemical formula 64]

[Organometallic complex] •X-1: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium •X-2: Pentamethylcyclopentadienyltrimethoxide titanium •X-3: Bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium •X-4: Tetraisopropoxytitanium (manufactured by Matsumoto Fine Chemical Co. Ltd.) •X-5: Diisopropoxybis(acetylacetonate)titanium (manufactured by Matsumoto Fine Chemical Co. Ltd.) •X-6 to X-8: Compounds having the following structures. [Chemical formula 65] The above X-1 and X-3 are compounds having photo-radical polymerization initiation capability.

[Crosslinking agent (free radical crosslinking agent)] •C-1～C-2: Compound with the following structure [Chemical formula 66]

[Polymerization inhibitor, migration inhibitor] •D-1 to D-7: Compounds with the following structure [Chemical formula 67]

[Additives] •E-1 to E-6: Compounds with the following structure [Chemical formula 68]

<Metal Adhesion Improver> •F-1 to F-6: Compounds with the following structure [Chemical Formula 69] In the above structural formula, Me represents a methyl group, and Et represents an ethyl group.

[Specified compounds] •G-1 to G-27: Compounds with the following structure [Chemical formula 70] [Chemical formula 71]

[Solvent] •NMP: N-methyl-2-pyrrolidone •EL: ethyl lactate •DMSO: dimethyl sulfoxide

<Evaluation> [Resolution evaluation] In each embodiment or comparative example, the prepared curable resin composition or comparative composition was applied to a silicon wafer by spin coating. The silicon wafer was dried on a heating plate at 100°C for 5 minutes to form a curable resin composition layer with a uniform thickness of 20 μm on the silicon wafer. In the example where "M" is recorded in the exposure condition, the curable resin composition layer on the silicon wafer was exposed using a stepper. The exposure was performed using light of the wavelength recorded in "Exposure wavelength nm" in the table, and using a mask of a fuse box with a scale of 1 μm from 5 μm to 25 μm. The exposure amount was set to the exposure amount that minimizes the minimum line width described later. In the example where the exposure condition is recorded as "D", exposure was performed using a direct exposure device (AdTech DE-6UH III). For exposure, laser direct imaging exposure was performed at a wavelength of 405nm so that the exposed portion became a line portion in a line and space pattern with a scale of 1μm from 5μm to 25μm. The exposure amount was set to an exposure amount that minimizes the minimum line width described later. The exposed curable resin composition layer was developed with cyclopentanone for 60 seconds and then rinsed with PGMEA (propylene glycol monomethyl ether acetate). Among the patterns obtained after development, the line width of the line pattern with the smallest line width among the line patterns that exposed the silicon wafer between the line patterns was taken as the "minimum line width" and evaluated according to the following evaluation criteria. It can be said that the smaller the line width, the better the resolution. For example, it means that the width of the metal wiring formed in the subsequent plating process can be miniaturized, which is a better result. The measurement limit is 5μm. The evaluation results are recorded in the "Resolution" column in the table. -Evaluation criteria- A: The minimum line width is 5μm or more and less than 8μm. B: The minimum line width is 8μm or more and less than 10μm. C: The minimum line width is 10μm or more and less than 12μm. D: The minimum line width is 12μm or more.

[Exposure sensitivity evaluation] A curable resin composition layer with a uniform thickness of 20 μm was formed on a silicon wafer by the same method as the above-mentioned resolution evaluation. In the example where the exposure condition is recorded as "M", the curable resin composition layer on the silicon wafer was exposed by a stepper using a mask having a mask portion (an example where the column of the developing conditions in the table is recorded as "negative") or a non-mask portion (an example where the column of the developing conditions in the table is recorded as "positive") with a diameter of 15.0 μm. The exposure wavelength is recorded in the "exposure wavelength nm" in the table. The exposure amount was varied in 50 mJ/ ^cm2 increments within the range of 50 to 500 mJ/ ^cm2 . In the example where the exposure condition is recorded as "D", laser direct imaging exposure was performed using a direct exposure device (AdTech DE-6UH III). The exposure wavelength was set to 405nm, and the exposure was performed in a manner to form a non-exposed portion with a diameter of 15.0μm. The exposure amount varied in increments of 50mJ/ ^cm2 within the range of 50 to 500mJ/ ^cm2 . Based on the minimum exposure amount for forming a hole pattern with a bottom diameter of 15.0μm, the sensitivity was evaluated according to the following evaluation criteria. The smaller the above minimum exposure amount (the higher the sensitivity), the better, and it can be said that the exposure sensitivity is excellent. The evaluation results are recorded in the "Sensitivity" column in the table. -Evaluation Criteria- A: The above minimum exposure amount is less than 100mJ/ ^cm2 . B: The minimum exposure amount is 100 mJ/cm ² or more and less than 150 mJ/cm ² . C: The minimum exposure amount is 150 mJ/cm ² or more.

From the above results, it can be seen that the hardening resin composition of the present invention has excellent resolution. Regarding the comparative compositions of Comparative Examples 1 to 6, the content of the specific compound is less than 10 ppm or exceeds 50,000 ppm relative to the total mass of the composition. It can be seen that the resolution of such comparative compositions is poor.

<Example 101> The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin substrate having the copper thin layer formed on the surface by spin coating, and dried at 100°C for 4 minutes to form a photosensitive film with a film thickness of 20μm, and then exposed using a stepper (Nikon Co., Ltd., NSR1505 i6). Exposure was performed at a wavelength of 365nm through a mask (a binary mask with a pattern of 1:1 line and space and a line width of 10μm). After exposure, heating was performed at 100°C for 4 minutes. After the above heating, development was performed with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds to obtain a layer pattern. Then, in a nitrogen atmosphere, the temperature was raised at a rate of 10°C/min to 230°C, and then maintained at 230°C for 120 minutes to form an interlayer insulating film for the redistribution layer. The interlayer insulating film for the redistribution layer has excellent insulation properties. In addition, semiconductor devices were manufactured using the interlayer insulating film for the redistribution layer, and the results confirmed that there were no problems with the operation.

without.

Claims (17)

A hardening resin composition comprising: a pre-driver selected from polyimide, polybenzoic acid,

A resin comprising at least one of the group consisting of an azole prodrug and a polyamide imide prodrug; an organic metal complex; and at least one selected from the group consisting of a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3), wherein the content of the aforementioned compound is 10 ppm to 100 ppm relative to the total mass of the composition, the content of the aforementioned resin is 50% by mass or more relative to the total solid content of the composition, and a solvent is included, and the total solid content concentration of the aforementioned curable resin composition is 40% by mass to 70% by mass.

In formula (1-1), formula (1-2) or formula (1-3), R ¹¹ and R ¹² each independently represent an unsubstituted aliphatic alkyl group having 1 to 7 carbon atoms, an aliphatic alkyl group having 1 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amine group, a tertiary amine salt structure, a quaternary ammonium group and an aliphatic heterocyclic group, or an aliphatic alkyl group having 2 to 7 carbon atoms as a substituent and having at least one substituent selected from the group consisting of a hydroxyl group, an alkoxy group, a thiol group and an alkylthio group, R ²¹ and R ²² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, R ³¹ and R ³² each independently represent an aliphatic alkyl group having 1 to 7 carbon atoms which may have a substituent, and R ³³ represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent. The curable resin composition as described in claim 1, wherein the aforementioned compound is a compound represented by any one of the following formulas (G-1) to (G-12),

The curable resin composition as described in claim 1 or claim 2 further comprises a photopolymerization initiator. The hardening resin composition as described in claim 1 or claim 2 further comprises a crosslinking agent. The curable resin composition as described in claim 1 or claim 2, wherein the aforementioned organometallic complex is a metallocene compound. The hardening resin composition as described in claim 1 or claim 2, wherein the metal contained in the aforementioned organic metal complex is at least one metal selected from the group including titanium, zirconium and einsteinium. The curable resin composition as described in claim 1 or claim 2, wherein the aforementioned organometallic complex has photo-radical polymerization initiation energy. The hardening resin composition as described in claim 1 or claim 2 is used to form a photosensitive film for negative type development. The curable resin composition as described in claim 1 or claim 2 is used to form an interlayer insulating film for a redistribution layer. A cured film, which is formed by curing the curable resin composition as described in any one of claim 1 to claim 9. A laminate comprising two or more layers of the cured films as described in claim 10, and a metal layer between any of the aforementioned cured films. A method for manufacturing a hardened film, comprising: A film forming process, wherein a hardening resin composition as described in any one of claim 1 to claim 9 is applied to a substrate to form a film. The method for manufacturing a hardened film as described in claim 12 includes: an exposure process for exposing the aforementioned film; and a development process for developing the aforementioned film. A method for manufacturing a hardened film as described in claim 13, wherein the exposure light used in the aforementioned exposure includes light with a wavelength of 405nm. The method for manufacturing a hardened film as described in claim 13, wherein the aforementioned exposure is based on laser direct imaging. The method for manufacturing a hardened film as described in claim 12 includes: a heating process, which is to heat the aforementioned film at 50°C~450°C. A semiconductor device comprising a hardened film as described in claim 10.